Top Catal (2011) 54:1224–1256

DOI 10.1007/s11244-011-9747-1

ORIGINAL PAPER

Catalysis in VOC Abatement

Satu Ojala • Satu Pitkäaho • Tiina Laitinen • Niina Niskala Koivikko • Rachid Brahmi •
Jana Gaálová • Lenka Matejova • Alexei Kucherov • Sanna Päivärinta • Christian Hirschmann •

Tuomas Nevanperä • Markus Riihimäki • Minna Pirilä • Riitta L. Keiski

Published online: 8 September 2011

 Springer Science+Business Media, LLC 2011

Abstract Volatile organic compounds (VOCs) are 1 Introduction

harmful to environment and human health. Catalytic oxi-
dation has been used in VOC abatement for over 60 years,
and it has proven to be an effective technology. A large
variety of VOCs set high demands for the treatment, and
therefore catalytic oxidation needs still to be developed
further. This paper reviews current aspects and future
research needs related to VOCs and catalytic VOC treat-
ment concentrating on solvent-based, chlorinated and sul-
phur-containing VOCs.
Keywords VOC emissions  VOC regulation  Effects
of VOCs  Catalytic oxidation
Catalytic abatement of volatile organic compounds (VOCs)
is an efficient, cost-effective and environmentally sound
way to treat these harmful emissions [1–3]. However, the
process is not straight-forward due to a large variety of
different VOCs. In fact, any hydrocarbon that is volatile at
room temperature or particular conditions of its use can be
included to the VOCs [4].
This review will start with defining of VOCs, giving
information on different legislation and with introducing
different health and environmental impacts of these emis-
sions. Later, the paper will concentrate on different

S. Ojala (&)  S. Pitkäaho  T. Laitinen  N. Niskala Koivikko  R. L. Keiski

S. Päivärinta  C. Hirschmann  T. Nevanperä  M. Riihimäki  e-mail: riitta.keiski@oulu.fi
M. Pirilä  R. L. Keiski
Mass and Heat Transfer Process Laboratory, University of Oulu, R. Brahmi
POB 4300, 90014 Oulu, Finland Laboratory of Catalysis and Corrosion, University of Chouaı̈b
e-mail: satu.ojala@oulu.fi Doukkali El Jadida, 1, Route de Ben Maâchou, 24000 El Jadida,
Morocco
S. Pitkäaho e-mail: rachid.brahmi@univ-poitiers.fr
e-mail: satu.pitkaaho@oulu.fi
T. Laitinen J. Gaálová  L. Matejova
e-mail: tiina.laitinen@oulu.fi Institute of Chemical Process Fundamentals AS CR v.v.i,
Rozvohov’s 135, 16502 Prague 6, Czech Republic
N. Niskala Koivikko e-mail: gaalova@icpf.cas.cz
e-mail: niina.niskala@oulu.fi
L. Matejova
S. Päivärinta e-mail: matejova@icpf.cas.cz
e-mail: sanna.paivarinta@oulu.fi
C. Hirschmann A. Kucherov
e-mail: christian.hirschmann@oulu.fi Zelinsky Institute of Organic Chemistry, Laboratory of Catalyst
Investigation, Russian Academy of Sciences, Leninsky Prospekt
T. Nevanperä 47, 334 Moscow, Russia
e-mail: tuomas.nevanpera@oulu.fi e-mail: akuchero2004@yahoo.com
M. Riihimäki
e-mail: markus.riihimaki@oulu.fi
M. Pirilä
e-mail: minna.pirila@oulu.fi

123
Top Catal (2011) 54:1224–1256
catalytic abatement methods of VOCs. It will give exam-
ples of the used catalytic materials, their advantages and
disadvantages. Two specific groups of VOCs will be
emphasized, namely, chlorinated (CVOC) and sulphur-
containing VOCs (SVOCs). These two groups are selected
since they have especially significant impact on health and
environment. In this review, the ‘normal VOCs’ are defined
as for example typical solvent emissions, that include
compounds containing carbon, hydrogen and oxygen.
Examples of these are alcohols, acetates and simple aro-
matic compounds.
1.1 Definition of VOC and Legislation
VOCs belong to the group of main air pollutants together
with sulphur oxides, nitrogen oxides, carbon monoxide,
ammonia and particulate matter (PM) [5]. Definitions of
VOC vary depending on the country and legislation in
question. For example different definitions are based on
vapour pressure, boiling points and reactivity of organic
species. According to European Solvent Emission Direc-
tive’s definition VOCs ‘‘shall mean any organic compound
having at 293.15 K a vapour pressure of 0.01 kPa or more,
or having a corresponding volatility under the particular
conditions of use. For the purpose of this Directive, the
fraction of creosote, which exceeds this value of vapour
pressure at 293.15 K shall be considered as a VOC’’ [4].
This is, however, not the only European definition, since
every Directive seems to have its own definition that is
slightly different to Solvent Emission Directive cited above
[4, 6–8]. For example Paint Directive [6] defines VOC as
following way: ‘‘Volatile organic compound (VOC) means
any organic compound having an initial boiling point less
than or equal to 250 C measured at a standard pressure of
101.3 kPa’’. The definition of the Solvent Emission
Directive is the most usual one in EU, but some European
countries, however, use their own definitions in certain
contexts. An example of this is Solvent Ordinance of
Switzerland that sets the maximum boiling point to 240 C
[9]. In the legislation of the U.S. Environmental Protection
Agency (EPA) ‘‘Volatile organic compounds (VOC) mean
any compound of carbon, excluding carbon monoxide,
carbon dioxide, carbonic acid, metallic carbides or car-
bonates, and ammonium carbonate, which participates in
atmospheric photochemical reactions’’ [10]. The partici-
pation in atmospheric photochemical reaction is also
mentioned in the VOC definition of VOC Protocol of
United Nations Economic Commission for Europe
(UNECE) and VOC definition of Canadian Authorities [11,
12]. Australia defined VOCs as ‘‘any chemical compound
that: (a) is based on carbon chains or rings, and (b) contains
hydrogen, and (c) has a vapour pressure greater than 2 mm
of mercury (0.27 kPa) at 25 C and 101.3 kPa, and
1225
includes any such compound containing oxygen, nitrogen
or other elements, but does not include methane, carbon
monoxide, carbon dioxide, carbonic acid, metallic carbides
and carbonate salts’’ [13].
The first VOC addicted directive of the Council of the
European Union (EU) was launched in 1999. The Council
Directive 1999/13/EC (Solvent Directive) states to replace
‘‘substances or preparations which, because of their content
of VOCs classified as carcinogens, mutagens, or toxic to
reproduction, are assigned or need to carry the risk phrases
R45, R46, R49, R60, R61 … by less harmful substances or
preparations within the shortest possible time’’ [4]. This
solvent directive gave the first limit values for VOC
emissions that were provided to be met by the year 2007.
The Directive sought to reduce VOC emissions from sol-
vent using installations by 67% as compared to the 1990
VOC levels. In 2001, the EU introduced the so-called NEC
directive. The directive 2001/81/EC [8] on national emis-
sion ceilings (NEC) shall improve the ‘‘protection of
human health and environment by reducing the emission of
acidifying and eutrophying pollutants and ozone precur-
sors.’’ Among other pollutants, strict VOC emission ceil-
ings for each country were set, which are to be reached
latest by 2010 [8]. This directive is related to Gothenburg
Protocol of UNECE LRTAP [11]. The limitations sug-
gested in the NEC Directives may be followed as they are
in the EU member countries or the member countries can
set more strict emission limitations than mentioned in the
Gothenburg Protocol that the NEC Directive is following.
In 2004, the Council Directive 1999/13/EC was amended
by the release of Directive 2004/42/CE [6]. The purpose of
the Directive 2004/42/CE is ‘‘to limit the total content of
VOCs in certain paints and varnishes and vehicle refin-
ishing products in order to prevent or reduce air pollution
resulting from the contribution of VOCs to the formation of
tropospheric ozone.’’ [6]. From now, the latest directive
affecting VOC was launched in 2008: Directive 2008/50/
EC on ambient air quality and cleaner air for Europe.
Annex X of the directive provides a list of VOCs recom-
mended for environmental air measurements [14]. At the
end of the year 2007 Integrated Pollution Prevention and
Control (IPPC) Directive (2008/1/EC) was suggested to be
included in the Industrial Emissions Directive (IE). The
Directive on Industrial Emissions 2010/75/EC was adopted
on 24th of November 2010. IE has entered into force on 6th
of January 2011 and has to be transposed into national
legislation by Member States by 7th of January 2013. IE
recasts seven existing Directives related to industrial
emissions into a single clear and coherent legislative
instrument. The recast includes the IPPC Directive, the
Large Combustion Plants Directive, the Waste Incineration
Directive, the Solvents Emissions Directive and 3 Direc-
tives on Titanium Dioxide [15].
123
1226
The VOC legislation in other than European countries
differs from country to country. For example Australia
does not have national air quality emission standards.
Instead, environment protection authorities in individual
States and Territories set such standards. For example, in
New South Wales, the Protection of the Environment
Operations (Clean Air) Regulation covers industrial air
emissions including VOCs. Regulations for VOCs are
specifically appointed to different types of facilities and
standards of concentration of VOCs for different premises
are mainly 20–40 mg/m3 in New South Wales Regulations
[13, 16, 17].
In USA the Clean Air Act (CAA) is the comprehensive
federal law that regulates air emissions from stationary and
mobile sources. Among other things, this law authorizes
EPA to establish National Ambient Air Quality Standards
(NAAQS) to protect public health and public welfare and
to regulate emissions of hazardous air pollutants such as
VOCs. Ambient air quality standards (AAQS) define clean
air and the maximum amount of a pollutant that can be
present in outdoor air without harm to the public health.
Both the Air Resources Board (ARB) in California and the
U.S. Environmental Protection Agency (U.S. EPA) are
authorized to set AAQS. The Federal Clean Air Act
requires the U.S. EPA to set outdoor air quality standards
for the nation. It also permits states to adopt additional or
more protective air quality standards if needed. California
has set standards for certain pollutants, such as PM and
ozone (O3), which are more protective of public health than
respective federal standards. California has also set stan-
dards for some pollutants that are not addressed by federal
standards such as hydrogen sulphide (H2S) and vinyl
chloride (C2H3Cl). Other air toxics are listed in California
Code of Regulations Titles 13 and 17. No standards have
been set for VOCs originating from non-industrial settings.
New Source Performance Standards (NSPS) on the regu-
lation of emissions from various types of industrial facili-
ties, 40 Code of Federal Regulations (CFR) 60 sets uniform
national emissions standards for over 60 source categories,
including fossil-fired steam generator, utility generators,
municipal waste combustors, cement plants, and others.
Emission standards, including VOCs, are specific to each
industry [18–21].
In Canada, there are VOC concentration limits defined
in Architectural Coatings Regulations (SOR/2009-264) and
Automotive Refinishing Products Regulations (SOR/2009-
197). The purpose of the regulations, made pursuant to
subsection 93(1) of the Canadian Environmental Protection
Act in 1999 (CEPA 1999), is to protect the environment
and health of Canadians by setting concentration limits
[12, 22–24].
The VOC legislation in African countries is not very
common. Other than VOC regulations can be found for
123
Top Catal (2011) 54:1224–1256
example from Morocco. Morocco has approved a draft
decree which sets standards for air quality and manner of
installation of monitoring networks. The decree has simi-
larities compared to the NAAQS in South Africa and it
includes regulations for benzene [25]. In South Africa most
sections of the National Environmental Management: Air
Quality Act (AQA) has been brought into effect. During
the recent years legislation on air quality has been revised.
In 2004 legislative reform in the form of the National
Environmental Management: Air Quality Act (No. 39 of
2004) (NEMAQA) has replaced the outdated Atmospheric
Pollution Prevention Act from the year 1965 (No. 45 of
1965) (APPA). The act provides the basis for setting
standards for both ambient air quality and emissions. Ini-
tiatives to counter emissions problems include a National
Framework for Air Quality Management (2007) which sets
a plan for achieving the objectives of the NEMAQA. The
national framework provides systems and procedures for
attaining compliance with AAQS and establishes national
standards on how provinces will monitor air quality. In
March 2010 the Department of Environmental Affairs
published national air quality standards which included
also regulations for benzene emissions [26–29].
In certain Asian countries VOC regulations exist. The
Republic of Korea amended a Clean Air Conservation Act
in 2007. Its aim is to prevent danger and damage to the
national health and environment due to air pollution, and to
manage and preserve properly the atmospheric environ-
ment. Regulation on VOCs is presented in Article 44.
Enforcement Decree of the Clean Air Conservation Act
amended in 2007 implements provisions of the Clean Air
Conservation Act. In that enforcement decree regulation on
VOCs can be found in Article 45 [30, 31].
China’s State Council promulgated its first-ever regional
air quality regulations on May 11, 2010. The regulations
direct the provinces to establish regional air quality plans
by the end of 2011 and full programs by 2015. Importantly
they require improvements in both air pollution monitoring
and control. There are specific provisions for all of the
major air pollutants—SO2, NOx, particulates and VOCs
[32].
Hong Kong (China) has been working towards air pol-
lution prevention already for rather long time. Merchant
Shipping (Prevention of Air Pollution) Regulation in Hong
Kong (China) imposes restrictions on the emissions of
harmful substances, such as ozone depleting substances,
nitrogen oxide, VOCs and sulphur oxide from ships in order
to implement Annex VI to the ‘‘International Convention
for the Prevention of Pollution from Ships, 1973’’ and to
align Hong Kong’s local legal requirements relating to air
pollution from ships with international standards [33, 34].
To reduce VOC emissions, the Government of Hong
Kong has implemented control measures to recover petrol
Top Catal (2011) 54:1224–1256
vapour released during petrol unloading and refuelling at
petrol stations, and to tighten emission standards of motor
vehicles in line with the EU standards. The VOC regula-
tion, effective from 1st April 2007 under the Air Pollution
Control Ordinance controls the VOC content in architec-
tural paints/coatings, printing inks and six broad categories
of consumer products (i.e. air fresheners, hairsprays, multi-
purpose lubricants, floor wax strippers, insecticides and
insect repellents) and requires emission reduction devices
to be installed on certain printing machines. The regulation
was amended in October 2009 to extend the control to
other products with a high VOC content including adhe-
sives, sealants, vehicle refinishing paints/coatings and
marine vessel as well as pleasure craft paints/coatings in
phases starting from 1st of January 2010 [35, 36].
The Japanese Ministry of the Environment announced
on April 8, 2005, that it would proceed with formulation of
a government ordinance to set emission standards for
VOCs under the Air Pollution Control Law, based on a
report submitted by the Central Environment Council, an
advisory panel to the Environment Minister. The report on
the introduction of regulations to control VOC emissions
proposed six types of facilities that should be regulated,
recommended that those which have potential VOC emis-
sions of 50 tons or more a year should be subject to the
regulations, and specified emission limits for each type of
facilities. The six categories are coating, adhesive bonding,
printing, chemical product manufacturing, solvent cleaning
and VOC storage [37].
As the reader can notice during the twenty-first century
several countries have adopted more restrictions for VOC
emissions. In Europe the implementation of the Directive
on Reduction of Motor Vehicle Emissions of VOCs (UN
ECE 1991) has resulted in the reduction of emissions of
certain organic compounds in 1990s. Also in Finland the
VOC emissions have been falling slowly in the 1990s.
Nevertheless, the obligation under the Geneva VOC pro-
tocol, which was signed in 1991, i.e. 30% reduction on the
1988 level of VOCs by 1999, proved to be more difficult to
attain than it was anticipated due to slow replacement of
old vehicles [38]. Furthermore, the reduction level for
VOC emissions sought in the Solvent VOC Directive was
not completely achieved, at least in Finland.
Even though all these regulations are steps towards
cleaner environment they also cause certain considerations
both to the VOC emitters and regulation authorities. As we
know, the emission limits for VOCs have dropped down
during the last years. To be able to confirm the compliance
of the emission limits corresponds to detecting VOC in
concentrations between ppm and ppb. It means that the
sensitivity parameter of the measurement equipment has to
be powerful. Measuring the concentration of the sum of all
single VOCs in an emission stream is doable with the
1227
commercial equipment available. However, determining
the concentration of all single VOCs (what means quali-
tative and quantitative information), is not straight forward,
even today. If the single concentrations are above
1–10 ppm, then commercial measurement devices are
available. Below concentrations of 1 ppm, the border of the
state of the art technology for industrial measurement
equipment is exceeded and no commercial measurement
devices are available. For some eminently harmful VOCs,
the emission limits are lying in that measurement-prob-
lematic region. This causes also a problem that complete
evidence concerning achievement of the strict VOC limits
is not available.
1.2 Environmental and Health Impacts of VOCs
The VOC emission limits set by different countries are
equal in one sense: all the countries want to limit the
harmful effects of VOCs to the environment and the human
health. Due to the large variety of these compounds VOCs
also have very varied harmful effects. In general, VOCs
have been reported to cause eye, nose and throat irritation,
headaches, loss of coordination, nausea but also more
problematic issues like damage to liver, kidney and central
nervous system. Some of the VOCs are highly toxic and
some have no known health effects, some are carcinogenic
and some of them are genotoxic. The time and level of
exposure affect the extent of a health effect [39, 40].
Assessing the general risk to the population, information on
long-term, low-level exposure to specific substances in the
environment is important, since the daily changes in the
emission levels can be high. For example, Uchiyama et al.
have proposed a 7-day or 28-day sampling for monitoring
concentrations of almost all VOCs [41].
In this paper the VOC types are divided into three cat-
egories. How the harmful impacts of CVOCs and SVOCs
differ from the general impacts of VOCs? For example,
SVOCs are typically very odorous at very low concentra-
tions. The odor threshold limits are so low that they do not
have yet a direct health impact on the people (See Table 1).
However, they may cause a major annoyance and thereby
affect the quality of life. It is also typical for SVOC
emissions that the emission levels vary day to day. It is
estimated that especially odorous emissions originating
from pulp and paper industry will always be a sensitive
subject between public and people living in areas sur-
rounding the mills [42]. In the case of CVOCs many of the
compounds are toxic at very low concentrations. For
example the International Agency for Research of Cancer
has classed carbon tetrachloride and chloroform in class
2B, that contains agents possibly carcinogenic to humans;
trichloroethylene (TCE) in class 2A, that are agents
123
1228
Table 1 Characteristics of certain SVOCs
Compound Boiling Odor threshold TWA
point (C) (ppb)
Methyl mercaptan 6 5–8 0.5 ppm
Dimethyl sulphide 37.3 1–20 10 ppm
Dimethyl disulphide 110 6–90 n.d.
n.d. not determined; TWA time weighted average (an average limit
value for the exposure during 8 h)
probably carcinogenic to humans and C2H3Cl in class 1,
that are agents carcinogenic to humans. One should not
forget that there are also normal VOCs classed to class 1
such as benzene and formaldehyde [43].
VOCs contribute to stratospheric ozone depletion. Many
of them are persistent, they survive the tropospheric
removal process and they reach the stratosphere. Chlorine
and bromine containing VOCs participate in the strato-
spheric photolysis and hydroxyl radical destruction that
release active ozone-destroying chain carriers. This means
stimulation of stratospheric ozone layer depletion and
Antarctic ‘ozone hole’ formation. VOCs have a crucial role
in ground level photochemical oxidant formation since
they control the rate of oxidant production in those areas
where NO levels are sufficient to maintain ground level
ozone formation. Ground level ozone is harmful to human
health and also it has effects on crops, plants, and trees
[40]. The ozone productivity is highest with aldehydes,
next with alkenes and lumped reactive aromatics [44].
Some gaseous emission compounds are not oxidized in the
atmospheric boundary layer and are transported into the
free troposphere where some longer-lived ones may accu-
mulate and thus contribute to the enhanced greenhouse
effect by absorbing solar or terrestrial infrared radiation.
Many organic compounds are not themselves radiantly
active gases, but they can act as secondary greenhouse
gases by being able to perturb the global distributions of
other radiantly active gases. Organic compounds can
behave also as secondary greenhouse gases by reacting to
produce ozone in the troposphere and increasing or
decreasing the tropospheric OH distribution and therefore
perturbing the methane distribution [40]. Environmentally
hazardous smog is formed when hydrocarbons react with
NOx and other airborne chemicals in the presence of sun-
light. As a result of this photochemical oxidation, ozone, a
primary component of smog is formed [45]. VOCs are also
precursors of secondary pollutants. Atmospheric oxidation
of biogenic and anthropogenic VOCs is one of the main
sources of carbonaceous aerosols (organic and black car-
bon) [46]. Secondary organic and secondary sulphate aer-
osol production is enhanced by aromatic species and
formaldehyde [44].
123
Top Catal (2011) 54:1224–1256
1.3 Emission Sources of VOCs
In general, air emissions can be originating either from
nature or from man-made so-called anthropogenic sources.
Natural emissions are originating from forests and plants
and it has been evaluated that they are especially emitted
from leaves. Major compounds originating from natural
sources are the terpenes [47]. The reduction efforts are
done to decrease the man-made emissions. These anthro-
pogenic emission sources can be further divided into two
categories namely stationary (point and area sources) and
mobile sources. Stationary sources include for example
industrial processes and gasoline distribution. Mobile
sources are related to road and off-road traffic, marine
transport etc. [41]. In addition to outdoor emissions one
should not forget the indoor emissions of VOCs. These are
originating for example from cooking and using of hair
spray, but also from furniture coatings etc. [48].
In Europe the NMVOC emissions have decreased by
51% during the years 1990–2008. The emissions of PCDD/
F, total PAH, HCB, HCH and PCB have decreased by 81,
60, 89, 86 and 76%, respectively. According to the emis-
sion values of NMVOC in 2008, it seems that EU-15
countries have reached the emission level agreed in
Gothenburg Protocol for 2010 emission ceilings. Of the
major pollutants only NOx reduction was not succeeded as
expected. In 1990 three largest NMVOC emitters in EU
were Germany, France and UK. In 2008 they were
Germany, Italy and France. Major emitters of dioxins and
furans in EU in 2008 were Italy and Poland that had,
however, managed to reduce the emissions between 1990
and 2008 by 32 and 25%, respectively. Major emitters of
PAH in 2008 were Spain and Belgium, major HCB emit-
ters Spain and UK and major PCB emitters Poland and UK.
In EU countries the major emission source of VOCs is the
solvent and product use (41%) and the second is the road
transport (16%). Between the years 1990 and 2008 the
solvent and product use sector managed to decrease VOC
emissions by 28% [5].
The emissions of VOC are varying a lot depending on
the industrial sector. In general, pharmaceutical industry
and e.g. dry-cleaners emits CVOCs, paint industry solvent-
based ‘normal’ VOCs, and wood-related chemical industry
SVOCs. The emissions are, however, always mixtures and
the concentrations depend strongly on the process-unit
where they are emitted. In Europe it was estimated that in
2000 about 120,000 sites produce VOC emissions. Of these
sites about 40% had installed a VOC abatement unit and
thus a great deal of sites had been left without any treat-
ment [49].
Volatile organic pollutants can be found also from waste
water. The reduction of these pollutants can be done by
several ways, for example pervaporation [50] or catalytic
Top Catal (2011) 54:1224–1256
wet air oxidation [51]. In some cases the treatment of
wastewater may shift the pollutant to the gas-phase and
change it as an air emission problem. It is not unusual that
waste water treatment plants cause odor annoyance to the
neighboring area. In these cases combination of water and
air treatment as a hybrid technology would give the best
and most economical solution for emission abatement.
2 Catalytic Oxidation of VOCs
The catalytic oxidation or incineration of VOC emissions
is classified as a secondary treatment method or a so-
called end-of-pipe technology. It can be carried out
technically in several different ways. The catalyst qualities
also differ largely—typically shaped catalysts are used in
industrial applications, but they may contain a variety of
different noble metals, metal oxides and mixtures of those
to fulfill the high abatement requirements. The following
chapters will give comprehensive examples of used cata-
lytic materials, preparation and use of structured catalysts.
The importance of catalyst qualities: activity (A), selec-
tivity (S) and durability (D), i.e. deactivation, are slightly
different in the cases selected on the focus areas of this
paper. The authors of the paper suggest, that in the case of
normal VOCs, the order of these features is A = D = S,
for CVOCs it is S [ D = A and for SVOCs D = S [ A.
The following chapter will give more explanation to this
issue.
2.1 Catalytic Materials Used
The most well-known and used solution is to use supported
noble metal catalysts in catalytic VOC oxidation. Several
industrial vendors of such the catalysts are available.
However, even if the noble metals are very active and
generally resistant to poisons they also have rather high
price. The current prices of noble metals can be found for
example from: www.platinum.matthey.com/pgm-prices,
www.scotiamocatta.com and www.ft.com/markets. In
addition, as in the case of CVOCs noble-metal containing
catalysts alone are not always selective enough. This is also
the case in the oxidation of SVOCs. This chapter will
concentrate now more on the special features of the before
defined three VOC classes and the catalyst development.
2.1.1 Normal VOCs
Due to the large variety of normal VOCs this chapter will
mainly concentrate on the catalytic treatment possibilities
of solvent emissions and fuel-related emissions. In general,
the oxidation of normal VOCs follows the reaction (1):
1229
Cx Hy þ ðx þ y=4ÞO2 ! xCO2 þ y=2 H2 O ð1Þ
According to our definition of normal VOCs, the main
reaction products are CO2 and H2O. Therefore, further
treatment of reaction products is typically not needed. The
catalytic oxidation of normal VOCs is quite simple and if
the temperature is selected high enough, no partial oxida-
tion products are formed. Figure 1 shows an example of
formation of partially oxidized compounds during oxida-
tion of n-butyl acetate over La-doped Pt–Al2O3 catalyst
while temperature is increased from room temperature up
to total oxidation temperature [3]. By-products of the cat-
alytic oxidation of n-butyl acetate have been studied also
e.g. over perovskites, over copper manganate and over
uranium oxide. The results of these studies are summarized
in Table 2.
For example, Lintz and Wittstock [52] found the for-
mation of the above-mentioned by-products at temperature
of 350 C when the T100 of n-butyl acetate was already
achieved. In the experiments, the amounts of by-products
started to decrease when the reactor length i.e. residence
time was increased. Due to the rather easy way to avoid by-
product formation, the authors suggest that activity is the
most important quality of the catalyst in the case of normal
VOCs. Therefore this chapter will put the main emphasis to
the activity of the catalysts.
The activity of a catalyst is typically evaluated by light-
off tests, where the conversion of the reactant(s) is fol-
lowed while the temperature is increased by a selected
heating program. The resulting S-shaped curves give a
good idea about the light-off point as well as total con-
version temperature. With the same curves also preliminary
evaluation of certain kinetic aspects and mass transfer
limitations can be done. According to Ertl et al. [53] con-
version alone, or conversion versus time, is useless as the
16
14
Concentration / ppm
12
10
8
6
4
2
0
0 100 200 300 400 500 600 700 800 900
Temperature / °C
Fig. 1 Evolution of formed organic partial oxidation products during
oxidation of n-butyl acetate over La-doped Pt–Al2O3 catalyst
123
1230
Table 2 Some examples of catalysts tested in n-butyl acetate total
oxidation and the by-products detected
Ref. Catalysts By-products
[73] Perovskites: Aldehydes, traces of butanol
LaMn2O3 (bulk) Acetaldehyde, propionaldehyde,
Ag/cordierite/ butyraldehyde
LaMn2O3
[74] U3O8 No organic by-products detected
[75] U3O8 No organic by-products detected
U3O8/SiO2
U3O8/SiO2
[52] Copper manganate Acetaldehyde, acetic acid, butanol,
butene, crotonaldehyde
measure of activity. Activity should be measured as a rate,
and it may be defined e.g. by the number of the catalytic
actions per unit time, or turnover rate, or turnover fre-
quency (TOF).
number of molecules of a given product
TOF ¼
ðnumber of active sitesÞ  ðtimeÞ
In heterogeneous catalysis it is often difficult to determine
the number of active sites, and thus the value is replaced by
the total area of the exposed catalyst. This replacement sets
a lower limit to TOF. By now, it has become more and
more common to use TOF as a measure of catalyst activity
in heterogeneous catalysis due to the advanced analytical
techniques; however, it is still applied most profitably to
single-crystal model catalysts [54].
The three main reaction mechanisms for derivation of
kinetic rate expressions for the oxidation of VOCs are
considered and discussed in literature [55–60], namely
Mars–van Krevelen mechanism (also called redox mecha-
nism since it presumes the remittent oxidation and reduc-
tion of the catalyst’s surface), Langmuir–Hinshelwood
mechanism and Eley–Rideal mechanism (last two are
derived for bimolecular reactions). The Mars–van Krevelen
mechanism assumes that in the first step (1) the oxygen
from the catalyst oxidizes the reactant from a gas phase
producing the reduced active site on the catalyst’s surface
and oxidation products which immediately leave the cata-
lyst’s surface. In the second step (2) the catalyst is reoxi-
dized by oxygen from the gas phase. The general reaction
scheme is following:
CO þ A ! C þ AO
C þ 0:5O2 ! CO
where CO is the oxidized active site, A the gas-phase
reactant, C the reduced active site and AO the product of
oxidation. The Langmuir–Hinshelwood mechanism
proposes that both reactants (oxygen and reactant
123
Top Catal (2011) 54:1224–1256
molecule) are adsorbed on the surface of the catalyst and
the adsorbed molecules undergo a bimolecular reaction
according to the following scheme:
A þ S $ AS ð5Þ
B þ S $ BS ð6Þ
AS þ BS $ CS þ S ð7Þ
CS $ C þ S ð8Þ
where A and B are reactants, S the adsorption site on the
catalyst’s surface, AS, BS and CS are surface complexes
on the catalyst and C is the oxidation product. The Eley–
Rideal mechanism assumes that only one reactant (oxygen)
is adsorbed on the surface of the catalyst and the second
one (reactant molecule) reacts with it directly from the gas-
phase without adsorption. The mechanism can be described
in the following way:
A þ S $ AS ð9Þ
B þ AS $ CS ð10Þ
CS $ C þ S ð11Þ
ð2Þ
There are several factors that may affect catalyst activity to
oxidize certain compounds. Examples of these are: the
active compound, loading [61] and oxidation state of the
active compound [62, 63], the washcoat material [62, 64],
the surface area of the catalyst and the dispersion of the
active material [65], the oxygen mobility and oxygen
storage capacity (OSC) of a catalyst [56, 66] as well as the
modifiers and promoters [67, 68], even precursor salts [69,
70]. Furthermore, variations in process operation condi-
tions such as in temperature, in pressure, and in gas mixture
composition influence catalyst activity [71]. Real VOC
emissions are usually mixtures of hydrocarbons, and in
mixtures, the compound that is the most difficult to oxidize
determines the rate of total oxidation [63].
In EU, the major emission sources of normal VOCs are
the solvent-using industry, such as painting and coating of
different products as well as refining, storage and distri-
bution of fuels. According to our experience, the emissions
of wood-coating industry (e.g. furniture manufacturers) are
mainly composed of n-butyl acetate and ethanol, but also
other alcohols and acetates are included [72]. These
emissions are typical solvent-VOC emissions and catalytic
oxidation of n-butyl acetate is studied e.g. over perovskites
[73], over U3O8 [74, 75], over doped noble metal catalysts,
ð3Þ Cu–Mn oxides, MnO2–MgO, CuxMg(1-x)Cr2O and Cux-
Cr2O4 [3] and over copper manganate [52]. It seems that in
ð4Þ
general, noble-metal-based catalysts are more active, but in
n-butyl acetate oxidation also Cu-based catalysts seem to
be very active. Reduction in the light-off temperature of
reaction in catalytic oxidation is more than 300 C when
compared with the T50 of non-catalytic oxidation of n-butyl
Top Catal (2011) 54:1224–1256
acetate. However, the noble-metal based catalysts are
typically more selective [3]. Musalik-Piotrowska et al. [73]
discovered that the efficiency of oxy-derivative oxidation is
higher than that of corresponding hydrocarbon over the
studied perovskite (LaMn2O3) catalysts. The reactivity of
the compounds decreased as follows: Acetone = butyl
acetates [ ethyl acetate [ toluene [ n-hexane.
Organic air pollutants emitted in industrial exhaust gases
usually present mixtures of VOCs of different chemical
characteristics. The ‘‘mixture-effect’’ in catalytic oxidation
is very difficult to predict beforehand, usually an inhibiting
effect and rarely promoting effect have been observed
when two-component mixtures were oxidized. N-Butyl
acetate oxidation was strongly inhibited by n-hexane on
bulk perovskite and by toluene and n-hexane on monolithic
perovskite. When toluene was added to the mixture, the
concentration of the intermediates was also higher as
compared to the oxy-derivatives oxidized separately on
both the tested perovskites. When n-butyl acetate was
oxidized with n-hexane over monolithic perovskite, no by-
products were detected even at 200 C. In addition, oxy-
derivates were inhibiting reactions of other hydrocarbons
in mixtures [73].
Another very significant VOC emission source is oil
refining industry. According to Caj Karlsson [76] from
Naantali Neste Oil Refinery in Finland, the typical VOC
emission sources are dispersed around the factory area.
Due to the large area, the emissions are impossible to
collect to one site and install there a treatment technology.
In Naantali refinery, the largest source of VOC emissions
are the light hydrocarbons emitted from crude oil. These
emissions are burned in underground flare. Estimated
fugitive emissions of the refinery site are around 1000
tonnes per year. The emission mixture contains mainly
C1–C5 hydrocarbons. They contribute around 70% of
emissions. Other constituents are olefins (alkenes), around
15% and benzene about 5% of total emissions. Information
on exact composition of emission is not available [76].
There exist a great amount of literature concerning meth-
ane oxidation, which is one organic compound affecting
strongly on global warming. Comprehensive reviews on
catalytic oxidation of methane are published for example
by Ciuparu et al. [71] as well as Gélin and Primet [65]. In
addition, in a strict sense, methane is not VOC, since it is a
gas in normal conditions. Therefore, this paper is not
concentrating on methane oxidation more. In general, with
normal VOCs, alkenes are easier to oxidize than alkanes
due to their higher reactivity [77].
In recent years another fuel-related aspect may begin to
affect VOC emissions. Notwithstanding the fact that fossil
fuels still report more than 95% of the global transportation
fuel market, biofuels production is rising almost 15% per
year, a rate over ten times that of oil. Under a growing
1231
pressure to improve domestic energy safety and combat the
advance of climate change, countries are now turning to
biodiesel and ethanol to meet mounting transportation fuel
demands. The European Community recently announced
the goal that biofuels will represent 10% of their trans-
portation fuel needs by 2020. Of all the current biofuels,
ethanol appears as the most popular and it is hotly debated.
Its production more than doubled between 2000 and 2005
being 2% of global fuel use. According to the Market
Research Analyst the world’s ethanol production will reach
75 billion litres in 2012. In spite of all production disad-
vantages, ethanol has a strong political support. Elected
officials have called for a greater expansion of E-85, a fuel
made of 85% ethanol and 15% gasoline. Although most
vehicles can utilize a 90:10 ratio of gasoline and ethanol,
automakers are now upping production of ‘‘flex-fuel’’ cars
that run on E-85. Comparing to traditional gasoline, the
problem of E-85 ethanol combustion is that it actually
augments the output of two different carcinogens namely
formaldehyde and acetaldehyde. In general, incessantly
rising number of cars using ethanol as a fuel thus neces-
sarily requires to reduce those emissions. Furthermore, the
data of binding authorities signalise that this vital exigency
is coming rapidly to our neighbourhood. The development
of suitable oxidation catalysts for ethanol is evidently of
importance [78]. The noble metal (Pt, Pd…) catalysts are in
general favourable for the control of emissions from eth-
anol-fuelled engines because of their higher activity in
complete ethanol combustion. Those materials are very
stable and indicate the advantage of good selectivity to
form CO2 [79–81]. The transient metal (V, W, Cr, Mn, Cu
or Co) oxides have been recognized as another alternative
for ethanol oxidation catalysts [82]. Acknowledged
example is a commercial mixture of MnO2 and CuO, called
hopcalite [83–85]. The interest of such materials consists in
lower price and higher resistance to poisons than in the
case of noble metals containing ones. Due to these reasons
Kovanda and colleagues [86–91] have put forward an easy
preparation mode of mixed oxide based catalysts by a
controlled thermal decomposition of hydrotalcite-like pre-
cursors. Those oxides display homogenous distribution of
the active components and both high surface area and a
good thermal stability. Furthermore, their activity in total
oxidation of ethanol is comparable with the best by now
known catalysts. A vast application potential of hydrotal-
cite-like precursors includes the role of promising model
systems permitting to give details about the relations
between acid–base or redox characteristics of solid phase
and catalytic activity in total oxidation of more or less
polar chemical compounds. Namely, easy modification of a
final precursor composition during the preparation leads to
materials with diverse physical chemical nature of the
surface [92, 93]. Gaálová et al. have used a sol–gel method
123
1232
of preparation and modification of mixed oxides, and they
found out that it gives better results in terms of homoge-
neity and OSC of the materials than coprecipitation
method. However, there is no linear function between OSC
and activity [92]. Mattos and Noronha [93] suggest that
modification of redox properties may be a strategy to avoid
undesirable by-products. They affirm that high OSC
favours the formation of acetate species, which could be
decomposed to CH4 and/or oxidized to CO2 via carbonate
species. On the other hand, a lower OSC of catalyst leads to
more important ethoxy species formation; these species can
be dehydrogenated and desorbed as acetaldehyde. And
finally they suppose that material such as Pt/Al2O3—
without noticeable redox properties—produces acetic acid,
perhaps because of acidic properties [93].
Gaálová et al. [94–96] have studied the effect of dif-
ferent promoters (Pt, Pd, U, La, and K) on the physical–
chemical and/or catalytic properties of the Co–Mn–Al
mixed oxides in the total oxidation of VOC. They used
toluene and ethanol as the model compounds. These nano
materials were prepared by thermal treatment (500 C) of
both groups the parent layered double hydroxide precursor
with Co:Mn:Al molar ratio of 4:1:1 and its modified pre-
cursors. The catalytic activity of all catalysts has very
similar order for oxidation of both VOC (order from the
most active catalysts to the less active one):
K [ U [ parent Co4MnAl [ La [ Pd [ Pt. The U and Pt
modified catalysts, as well as the parent, induced no reac-
tion intermediates during toluene oxidation. However, in
the presence of Pd, K and La modified catalysts, very
undesirable reaction intermediate (benzene) was formed.
Therefore, such catalysts cannot be recommended for cat-
alytic combustion of toluene. Concerning ethanol oxidation
selectivity, some amount of reaction intermediates, mainly
acetaldehyde, were found for all catalysts except 3% La/
Co4MnAl [94–96].
O’Malley and Hodnett [97] studied the oxidation of
VOCs over Pt-catalysts supported on b-zeolite, mordenite,
silica and alumina, and discovered that the reactivity was
as follows: alcohols [ aromatics [ ketones [ carboxylic
acids [ alkanes although some overlapping was observed.
The more reactive alkanes were more readily oxidized than
the less reactive carboxylic acids. They also postulated that
bond dissociation enthalpies are the key parameters in the
determining the reactivity of substrates and the slow step is
cleavage of the weakest C–H bond in the substrate (with
the aid of the catalyst). The primary factor in determining
the reactivity of VOCs in oxidation is the strength of the
weakest C–H bond in the structure followed by further
steps that may involve free radical chemistry. Compounds
with a single weak C–H bond are more readily destroyed
by oxidation on a supported Pt catalyst. Other factors, such
as adsorption, may also become important, especially in
123
Top Catal (2011) 54:1224–1256
conditions where the VOC reacts at a very low temperature
[97].
2.1.2 CVOCs
The catalysts applied in the CVOC destruction should be
highly active at relatively low temperatures, maintain high
resistance towards deactivation by chlorine and its deriv-
atives and have high selectivity towards CO2 and HCl
production. Many of CVOCs belong to the R-labelled
compounds that mean very low emission limits, such as the
emission limit for R40 compounds that is 20 mh Nm-3,
and therefore the activity of a catalyst is a very important
issue. Even if, CVOCs are more difficult to oxidize than
normal VOCs, and the catalyst deactivation by chlorine
should not be forgotten, the selectivity towards HCl for-
mation is considered as a major feature in this case. This
selection is done based on the fact that with poor selectivity
the oxidation products of CVOCs may contain highly toxic
by-products that are more harmful than the initial emission
compounds.
The reactivity of CVOCs in the catalytic oxidation, as
well as the distribution of the reaction products, depends
strongly on the catalyst used and the chemical structure of
the oxidized compounds [97–99]. In general, independently
on the catalyst used, the catalytic destruction of chloro-
alkenes is more difficult than that of chloroalkanes due to
higher bond energy of C–Cl in chloroalkenes [57, 99–103].
Overlapping of the chlorine p-orbital with the p-electron
system of double bond increases the bond order and its
strength. Selectivity comes very important in the case
where the emission compounds contain more chlorine
atoms than hydrogen atoms. In this case CVOCs cannot be
totally converted by air to the most desirable chlorine-
containing product i.e. HCl. Therefore even more toxic
products such as chlorine (Cl2) and phosgene (COCl2) can
be formed. Incomplete oxidation can create a variety of
other by-products. Undesired formation of CO as well as
formyl chloride (HClCO), C2H3Cl and perchloroethylene
(PCE, C2Cl4) has been observed in the case of oxidation of
C1 and C2 chlorinated compounds. Highly toxic dioxins
and furans (PCDD/F) can also be formed unintentionally
during the low molecular weight CVOC incineration [104,
105]. Depending on the catalyst, both noble-metal and
metal-oxide catalysts can be active in the Deacon reaction
leading to the formation of molecular chlorine and unde-
sired chlorinated compounds. To improve selectivity
towards HCl, either a hydrogen-rich additive or water
vapour should be added to the feed stream. It has been
reported that the presence of water, not only promotes the
selectivity towards environmentally desirable reaction
products, HCl and CO2, but it also affects positively the
CVOC conversion [98–100, 106, 107].
Top Catal (2011) 54:1224–1256
Studies on CVOCs oxidation over different types of
catalysts, e.g. supported noble metal catalysts, metal oxi-
des, gold and V2O5 catalysts, zeolites, perovskites, and
zirconia–alumina, show that noble metal catalysts are more
selective than metal-oxide-based catalysts or perovskites
[97–99, 106–116]. Besides the active component, destruc-
tion of CVOCs depends on the catalyst support. For
example for saturated CVOCs Brønsted acidity plays an
important role on alumina-based catalysts since the
adsorption of CVOC on catalyst surface occurs at acid sites
through hydrogen bonding between Cl and surface proton.
On titania supported catalysts the radical initiation is sug-
gested; light-off temperature is directly related to the
energy required for a radical dissociation of the CVOC to
be oxidized [114]. A Langmuir–Hinshelwood competitive
adsorption model was proposed to describe the PCE oxi-
dation over (3:1)PtRh/three way catalyst [56].
As it was described before, mixing of different VOCs
may result in different oxidation efficiencies as estimated
with single compounds. Generally over noble metal cata-
lysts the presence of hydrogen-rich compounds (e.g. water
or VOC), has a beneficial effect on the selectivity towards
HCl but also the conversion of CVOC may be enhanced.
On the other hand, CVOCs usually inhibit the oxidation of
the non-chlorinated VOCs added [98–100, 106, 110, 114,
116–119]. Enhanced destruction of CVOC is dependent on
the VOC used, e.g. unsaturated VOCs can strongly enhance
the oxidation of unsaturated CVOCs while with saturated
VOCs the effect is smaller [114].
Pitkäaho et al. studied the mixture effect when
dichloromethane (DCM) and PCE were oxidized in two-
component mixtures in the presence of dimethylformam-
ide (DMF), ethylene glycol monoethyl ether (EGEE),
ethanol or ethylene (only with PCE) in moist (water
1.5 wt%) conditions over the (1:1)PtPd/Al2O3–Ce2O3
catalyst. DMF was found to affect positively the DCM
conversion. In moist conditions the effect of DMF on
selectivity towards HCl was negative, especially at low
temperatures but in dry conditions and at high tempera-
tures ([460 C) the selectivity was enhanced in the
presence of DMF. Both, ethanol and EGEE affected
negatively the DCM conversion and selectivity indicating
a competitive reaction mechanism. Water (1.5 wt%)
clearly enhanced the oxidation of DCM and had a posi-
tive effect on the HCl selectivity as it increased the HCl
yield at 500 C from 37 to 68%. Additives tested during
these experiments showed only minor impacts on the PCE
conversion. Both DCM and PCE inhibited DMF oxidation
but in EGEE destruction, the presence of CVOC did not
have any influence [119]. In earlier studies [110, 111,
117] the catalytic oxidation of CVOCs in VOC mixtures
has shown to inhibit VOC oxidation indicating that the
most important role in the reaction pathway may be a
1233
competition between the reacting compounds in the
mixture to the same active sites.
Wang et al. [118] found in their studies that over plat-
inum supported on alumina toluene did not enhance the
oxidation of DCM due to reactions occurring at different
active sites; oxidation of DCM occurs on the acid sites
while the oxidation of toluene occurs on the platinum sites.
Instead, they found that the selectivity towards HCl was
improved and the formation of CH3Cl was decreased due
to water generated in toluene oxidation [118]. Orbay et al.
[120] tested a commercial (3:1)PtRh three way catalyst and
they found that an experiment with PCE under typical
oxidation conditions without a H2 source showed insig-
nificant PCE conversion but as the H2/O2 ratio was
increased, optimum being 2:1, the PCE conversion
increased reaching about 90% at 400 C. In their further
study [56] propane was tested as a hydrogen source in
thermocatalytic destruction of PCE and it was found that
the PCE conversion was significantly increased. At 450 C
conversion close to 100% was observed with 20% of
oxygen and 2% of propane in the feed. In the absence of
oxygen, even higher conversions were observed but the
catalyst suffered significant deactivation in less than one
hour. Orbay et al. [120] suggest that deactivation occurs
due to certain PCE reduction intermediates that can mask
the catalyst surface and/or chlorine poisoning. In oxidative
conditions the deactivation was not so significant.
In the TCE mixture tests, several additives have been
found to enhance the conversion of TCE. Gonzales-
Velasco et al. has reported the enhancement of TCE oxi-
dation over alumina-supported Pt or Pd in the presence of
water, hexane and toluene [107, 109]. Musialik-Piotrowska
and Syczewska [110] concluded in their study that each
VOC (toluene, n-heptane, ethanol, ethylacetate, acetone,
and methylethylketone) added to the reaction mixture
strongly enhanced TCE oxidation over platinum. Over
palladium, only toluene and ethanol had a promoting effect
on TCE oxidation, and over perovskite, each compound
inhibited TCE oxidation [110]. Musialik-Piotrowska also
reported results of Pt–Pd based metallic monolith catalysts:
T50 for TCE and trichloromethane (TCM) was achieved at
420 and 330 C, respectively. In binary mixtures the added
VOCs enhanced the conversion of CVOC lowering the T50
temperature maximally by 50 C in the presence of acetone
for TCE and by 20 C in the presence of n-hexane for
TCM. TCE or TCM had no effect on the combustion of
toluene but they inhibited the oxidation of n-hexane [121].
In recent years ceria-based catalysts have been investi-
gated in CVOCs oxidation [58, 99, 121–123] because they
are demonstrated to be very active in VOC oxidation due to
the unique features of CeO2—its high oxygen-storage
capacity and facile reducibility of Ce4?/Ce3? compared to
other fluorite-type oxides [124]. The mechanism of VOC
123
1234
oxidation reactions over ceria (CeO2) is generally consid-
ered to be a redox type mechanism (Mars–van Krevelen),
in which the key steps are the supply of oxygen by the
readily reducible oxide and its re-oxidation by oxygen [58].
Ceria-based catalysts have been studied mainly in oxida-
tion of C1 and C2 chlorinated hydrocarbons, mainly DCM,
1,2-dichloroethane (DCE), CCl4, TCE and PCE. Dai et al.
[101] reported a CeO2 catalyst with high catalytic perfor-
mance at low temperature (T90 value for PCE was 260 C
and DCM 160 C), but it was not thermally stable and
deactivated in few hours due to strong adsorption of HCl
and Cl2 species. These reasons led to the modification of
CeO2 with other metal oxides, especially with ZrO2. The
partial substitution of Ce4? with Zr4? in the lattice of CeO2
leads to improvements not only in catalyst’s OSC and
redox properties, but also its thermal resistance and cata-
lytic activity at lower temperatures as well [125–127].
Ceria-zirconia mixed oxides have been systematically
studied by Gutiérrez-Ortiz et al. [56] and De Rivas et al.
[122, 123]. Gutiérrez-Ortiz et al. [56] investigated ceria,
zirconia and a set of several Ce–Zr mixed oxides in DCE
and TCE oxidation under dry conditions. Ce0.5Zr0.5O2 and
Ce0.15Zr0.85O2 showed the highest catalytic activity. A
reason of better catalytic performance is that the insertion
of ZrO2 into the cubic CeO2 resulted in the distortion on
the mixed oxide structure, which allows greater lattice
oxygen mobility. Consequently, the reduction process was
no longer confined to the surface but extended deep into the
bulk. Hence, the light-off temperatures of the chlorinated
hydrocarbons significantly decreased. Moreover, it was
revealed by NH3-TPD that the higher content of ZrO2
presented in ceria–zirconia mixed catalysts, the higher total
acidity is. Therefore, the highest catalytic activity of these
two catalysts (Ce0.5Zr0.5O2 and Ce0.15Zr0.85O2) was
attributed to a suitable combination of both—(i) surface
acidity and (ii) a higher mobility and accessibility of the
lattice oxygen. Thus, it is believed that the low temperature
catalytic combustion over ceria–zirconia mixed oxides
involves the participation of surface and lattice oxide
anions via Mars–van Krevelen cycles, which can efficiently
attack the chlorinated compound adsorbed on acid sites.
The selectivity of these types of catalysts is more contro-
versial. The major oxidation products were CO2, HCl and
Cl2. Besides that, trace amounts of undesirable by-prod-
ucts, namely C2H3Cl (in DCE oxidation) and tetrachloro-
ethylene (in TCE oxidation) together with CO were
detected at mild temperatures (250–450 C). The selec-
tivity toward CO2 and Cl2 was favoured with an increasing
ceria content in mixed catalysts due to relative high activity
of ceria in the oxidation of CO to CO2, and in the oxidation
of HCl to Cl2 by the Deacon reaction.
De Rivas et al. studied the behaviour of thermally aged
Ce–Zr mixed oxides (at 550, 750 and 1000 C) in the
123
Top Catal (2011) 54:1224–1256
catalytic oxidation of DCE and TCE [122] and the influ-
ence of water and H-rich additives (water, toluene and
hexane) in the mentioned catalytic systems [123]. An
increase in the calcination temperature of Ce–Zr mixed
oxides led to a progressive decrease in the catalytic activity
as a result of the modifications provoked by induced
thermal aging—decrease in surface area, larger crystal
sizes, reducibility at higher temperatures and loss of acid
sites. Ce0.5Zr0.5O2 and Ce0.15Zr0.85O2 showed the best
resistance to deactivation with oxidation temperatures still
notably lower in comparison with the homogeneous reac-
tion even after calcination at 1000 C. An average shift in
T50 values was 25–35 C (when catalysts aged at 750 C)
and 40–50 C (when aged at 1000 C). Reaction selectivity
was also affected by thermal aging since the deep oxidation
ability was decreased. The yield of incomplete combustion
products, namely CO and chlorinated by-products, was
favoured. However, an interesting feature of deactivated
samples was that they partially inhibited the formation of
molecular Cl2 in favour of HCl, because the Deacon
reaction was not significantly activated. In the presence of
additional H-rich compounds in the feed stream the cata-
lytic activity of Ce–Zr mixed oxides was negatively
impacted due to the blockage and/or competition for
actives sites. On the other hand, the increased presence of
hydrogen atoms in the stream notably promoted the
selectivity to HCl instead of molecular Cl2. The catalytic
behaviour of a commercial catalyst based on Ce–Zr mixed
oxides was described by Willinger et al. [55]. The com-
mercial 3:1 (w/w) PtRh catalyst on CeO2–ZrO2 washcoat
supported on an alumina monolith was investigated in PCE
oxidation in the presence of propane as the hydrogen
source.
Gutiérrez-Ortiz et al. [102] reported that the incorpora-
tion of small amounts of zirconium in a MnOx catalyst can
improve its catalytic performance in oxidation of CVOCs.
They investigated DCE and TCE oxidation over a set of
several Mn–Zr mixed oxides, ZrO2 and Mn2O3. The Mn–
Zr mixed oxides led to noticeably higher activity, which
was ascribed to the manganese content, with respect to
pure ZrO2 and Mn2O3. A substantial surface acidity in
combination with readily accessible active oxygen species
were the catalytic properties responsible for the high
activity of Mn–Zr mixed oxides. Hence, the Mn0.4Zr0.6O2
was found to be the most active for the oxidation of both
chlorinated aliphatic hydrocarbons with a T50 value around
305 C and 315 C for DCE and TCE oxidation, respec-
tively. The major oxidation products were CO2, HCl and
Cl2. The yield of undesired Cl2 and by-products (again
C2H3Cl and PCE) depended on the nature of the chlori-
nated feed and on the catalyst composition. It was found
that Cl2 formation was significantly favoured in TCE
decomposition in comparison with DCE oxidation.
Top Catal (2011) 54:1224–1256
Besides, concerning the catalyst composition it could be
concluded that the formation of Cl2 was promoted with a
higher Mn loading in the catalyst. This fact was related to
the high activity of manganese for the Deacon reaction. On
the other hand, selectivity values to CO2 were close to
100%. Similarly to Ce–Zr mixed oxides, according to
Gutiérrez-Ortiz et al. [102], acid sites play a key role in
controlling the decomposition of chlorinated compounds
over acidic catalysts since they act as effective chemi-
sorption sites for such compounds. Accordingly, it was
suggested that the first stage of the oxidation process is the
adsorption of the chlorinated molecule on an acid site,
which subsequently can be attacked by mobile oxygen
species from the Mn–Zr mixed oxides through the Mars–
van Krevelen mechanism. It is known that at a lower
temperature range electrophilic oxygen species are the
catalytically active species for the total oxidation process.
However, at higher reaction temperatures the amount of
electrophilic oxygen species decreases. Thus, the oxidation
reaction proceeds increasingly under participation of
nucleophilic lattice oxygen species via the Mars–van
Krevelen reaction mechanism. In this context, it is believed
that in the high temperature range the disperse MnOx
phase, present mainly in the mixed oxides with a high
amount of manganese, is catalytically more active than
crystalline MnOx phases. In other words, the catalysts with
disperse MnOx phases are easier to reduce and are char-
acterized by a high defect concentration and high oxygen
mobility [59, 128].
Mn and/or Cu oxides based catalyst are very active in
VOCs [129], CO [130] and NOx [131] abatement. But only
a few studies were done over these types of catalysts in
CVOCs oxidation. Vu et al. [132] investigated 5 wt%
(Mn ? Cu)/TiO2 supported catalyst in the oxidation of
chlorinated aromatic compound, chlorobenzene (CB). The
catalytic tests proved that MnCuOx/TiO2 was very active
for chlorobenzene oxidation since the total conversion was
achieved. At 350 C chlorobenzene was exclusively con-
verted into H2O, CO2 and Cl2 without formation of any
other chlorinated by-products. The T50 and T100 values
were 275 and 350 C, respectively. Moreover, no deacti-
vation was observed after 5 days of testing. This perfor-
mance was attributed to the formation of the Mn1.6Cu1.4O4
spinel phase. However, at lower temperatures the catalyst
showed slight deactivation before a steady-state was
reached. In a long-term catalytic test at 300 C, the CB
conversion decreased and stabilized at 75% after 5 h and a
small amount of HCl and CO were detected. The reason
why HCl was not detected at temperatures higher than
350 C was explained by the Deacon reaction. The SEM/
EDS analysis revealed the presence of Cl2 uniformly dis-
persed on the catalyst surface. The formation of oxichlo-
rinated copper and manganese species (MnCuOx-aCl2a/
1235
TiO2) were presumed to be responsible to the catalyst
partial deactivation. The catalyst regeneration under air at
350 C allowed recovering the initial catalytic activity in
spite of the fact that chlorine was not completely removed
from the catalyst.
2.1.3 SVOCs
Catalytic oxidation of SVOCs is not very widely spread
research topic and this is why we have included in this
chapter also some results concerning other gaseous sul-
phur-containing compounds such as H2S and methyl mer-
captane (MM). These two compounds are very often
present in the emissions were SVOCs are observed. One
reason to small research interest on catalytic oxidation of
SVOCs may be the odorous nature of sulfur-containing
compounds, but also the fact that catalytic materials can be
deactivated by sulphur. High activity of a catalyst in the
case of SVOCs oxidation may cause certain problems.
Normally in SVOC oxidation the desired reaction products
are CO2, SO2 and H2O. In the case of noble metals, such as
platinum, it has been seen that SVOCs can be oxidized to
SO3 instead of SO2. SO3 is problematic, since it is an
unstable compound that reacts easily with H2O forming
sulphuric acid. In addition to catalysts this is problematic to
the construction materials used in the abatement system
[133–137]. Figure 2 shows an example of a heat exchanger
blocked due to acid corrosion. This issue shows how
important it would be to find a catalyst that is selective
towards SO2 formation. However, since selectivity got the
main emphasis in the case of CVOCs we will concentrate
here on the durability issues or deactivation of the
catalysts.
Fig. 2 A heat exchanger blocked due to acid corrosion
123
1236
Catalytic oxidation of MM has been studied e.g. by Ross
and Sood [138], Dalai et al. [139], Chu and Horng [140]
and more recently by Kastner et al. [141, 142] and Ojala
[3]. Ross and Sood [138] studied MM oxidation
(1000 ppm) over a cobolt molybdate catalyst at a temper-
ature range of 140–420 C. They did not find significant
changes in catalytic activity although the surface area of
the catalyst was decreased during the experiments. Kastner
et al. [141, 142] studied H2S and MM oxidation over coal
fly ash and wood ash. H2S formed elemental sulfur and
MM was oxidized to DMDS. Further oxidation of DMDS
over coal fly ash and wood ash did not take place. Wang
and Weng [143] carried out a study on DMDS oxidation
over eight different metal oxides (CuO, ZnO, Cr2O3,
MoO3, MnO2, Fe2O3, Co3O4 and NiO). They also tested
nine possible promoters (oxides of Mo, Cr, Ni, Mn, La, Fe,
Co, Sr and Zn). CuO supported on c-Al2O3 with the MoO3
promoter was found to be the most active one. They also
compared their catalyst to a Pt/c-Al2O3 catalyst and
observed approximately a 70 C decrease in T50 and
*100 C decrease in T100 with the CuO–MoO3 catalyst.
In MM oxidation over cobalt molybdate Ross and Sood
[138] observed the following reaction products at a tem-
perature level of 300 C: DMDS and water (main reaction
products), SO2 (about 25% compared to fed MM) and
traces of methanol, formaldehyde, ethyl methyl disulphide,
ethyl mercaptan and CO2. Methanol formation was
enhanced when water was present, and the formation of
ethyl methyl disulphide was increased at higher initial MM
concentrations. However, at temperatures [400 C mostly
SO2, CO2 and H2O were present. Dalai et al. [139] found
out that when MM was oxidized over activated carbon
(50–175 C, 122–364 kPa, O2:MM 1.1–1.33 times stoi-
chiometric value) the main reaction products were DMDS
and water, while CO2 was produced in small amounts. CS2
and (CH3)2S (DMS, dimethyl sulphide) were produced at
200 C in trace amounts. The 99.99% conversion of MM
was achieved at temperatures [100 C. Unfortunately,
catalyst deactivation was observed.
Ojala [3] tested different Pt and Pd-containing catalysts
supported on Al2O3 as well as MnO2–MgO, CuxMg(1-x)
Cr2O and CuxCr2O4 in oxidation of MM and DMDS. It was
seen that Pd-containing catalysts were slightly more active
in MM oxidation compared to monometallic Pt catalysts.
Addition of CeO2 improved further the oxidation activity
of the catalyst [3]. It is known that CeO2 has good OSC and
it increases also oxygen mobility of a catalyst [67]. Inter-
estingly Pd-catalysts have proven to be more active in
methane oxidation than Pt-catalysts as well [66]. Methyl
mercaptan and methane are quite similar molecules, since
in MM one hydrogen atom is replaced by the –SH–group.
In DMDS oxidation the differences between noble metal
catalyst activities were small, except CeO2 addition to
123
Top Catal (2011) 54:1224–1256
Pt-catalyst decreased the total oxidation temperature
almost by 100 C. When the activities of tested metal oxide
catalysts were compared to noble metal catalysts, it was
seen that metal oxide catalysts were superior. Observed
T100 and T50 temperatures were around 100 C less than
with the noble metal catalysts. However, it is important to
notice that the tested noble metal catalysts were metallic
monoliths and metal oxide catalysts were small spheres.
Catalytic experiments also showed that at lower tempera-
tures partial oxidation products are formed. In the case of
incomplete MM oxidation, DMDS was the major by-
product. Other compounds observed were DMS and H2S.
In the case of MM oxidation the by-products were DMS
and H2S. In general, slightly higher amounts of by-products
were observed in MM oxidation than in DMDS oxidation.
Less by-product were formed over a Pt/Al2O3 catalyst in
MM oxidation and over a CeO2-doped Pd/Al2O3 catalyst in
DMDS oxidation [3]. The formation of DMDS was also
observed in pilot experiments carried out earlier [133]. In
general, the formation of DMDS as a by-product of MM
oxidation is observed also in the studies of Kastner et al.
[142], Martı́nez et al. [144] and Dalai et al. [139]. At
around 350 C MM and DMDS are not fully oxidized, and
it is suggested [144] that the mechanism of oxidation
includes the formation of methylthiyl radicals (CH3S),
which further react to form DMDS. Kastner et al. [142]
have proposed a potential mechanism for the oxidation of
MM: They believe that if the R group is a methyl group,
oxygen is not capable of reacting with R-SS-R or R-S-R.
Therefore, there is no further reaction for that, and this thus
leads to the formation of DMDS from MM. This could be
avoided when the temperature is increased.
A catalyst is not consumed during the reaction, and by
this definition it should last forever. In real life, a catalyst
loses its activity during the time of the usage i.e. it deac-
tivates. Deactivation is a result of the removal of the active
sites from a catalyst surface, which can occur through a
number of different mechanisms, both physical and
chemical [145]. Table 3 summarizes the different mecha-
nisms of catalyst deactivation.
A catalyst with good stability will only change very
slowly over the course of time under conditions of use.
Some of the things that lead to a progressive loss of
activity or selectivity or mechanical strength are as fol-
lows [54]:
– Coke forms on some catalysts through the involvement
of unwanted reactions of hydrogenolysis, polymeriza-
tion, cyclization, and hydrogen transfer;
– Reactants, products or poisons may attack active agents
or the support;
– Volatile agents, such as chlorine, may be lost during
reactions such as reforming;
Top Catal (2011) 54:1224–1256
Table 3 Mechanisms of catalyst deactivation [252]
Chemical
– Poisoning: irreversible adsorption or reaction on/with
the surface
– Inhibition: competitive reversible adsorption of
poison precursor(s)
– Poison induced reconstruction of catalytic surfaces
– Physical/chemical blockage of support pore structure
– The crystals of a deposited metal may become enlarged
and regrouped. A change in the crystalline structure of
the support can cause a loss of mechanical strength; and
– Progressive adsorption of trace poisons in the feed or
products may reduce activity.
Sulphur is known to be a catalyst poison. However, the
poisoning can be reversible [78] and it is dependent on
temperature (e.g., Chu et al. [146]). The oxidation of
SVOCs may cause the deactivation of the catalyst during
the time of usage. There are a number of possible deacti-
vation mechanisms due to sulphurous compounds. For
example, DMDS may adsorb on catalytic surfaces, but as
discussed before, the possible formation of SO3 during the
oxidation reactions (of e.g., H2S, MM and DMDS), too,
may cause e.g., the sulphating of the support [136, 139,
147–149]. It is reported that Pt in particular is very active
in catalyzing the SO2 reaction to SO3 and probably thereby
sensitive to the sulphation of the support [136, 137]. In
addition, H2S observed in the oxidation of MM and DMDS
may bond very strongly to the active sites and form stable
surface metal sulphites [136].
Chu et al. [146] studied the poisoning of a MnO/Fe2O3
catalyst e.g. in DMDS oxidation and found out that sul-
phur-poisoning was dependent on the reaction temperature.
The deactivation was not significant when the temperature
exceeded 350 C. Jones et al. [136] studied methane oxi-
dation over Pt, Pd and Rh catalysts supported on Al2O3 in
the presence of reduced sulphur compounds (e.g. MM).
They observed the deactivation of all the tested catalysts,
of which the Pd catalyst was less deactivated. The regen-
eration in reducing conditions recovered, at least partly, the
activity of Pd and Rh catalysts, but with the Pt catalyst
agglomeration was observed and the regeneration was seen
as very difficult. Lee and Rhee [150] found out that Pt–Pd
bimetallic interaction (supported on beta zeolite) could
1237
Thermal Fouling Mechanical
– Sintering (redispersion) – Carbonaceous deposits – Thermal shock
– Alloying (coking) – Attrition
– Support changes – Small particulate deposits – Mechanical
(masking) breakage
– Noble metal-base metal
interactions
– Metal/metal oxide-support
interactions
– Oxidation (alloy formation)
– Noble metal surface
orientation
– Metal volatilization
improve resistance to irreversible sulphur adsorption and
sulphur-induced coke formation during isomerization of
n-hexane. A lot of research has been carried out concerning
the deactivation of different catalysts with SO2 (e.g., Fer-
randon et al. [151]). Interestingly, SO2 sometimes also has
beneficial effects. For example Corro et al. [152] have
reported on the promoting effect of SO2 on propane oxi-
dation over Pt/Al2O3 catalyst at temperatures higher than
300 C. Skoglundh et al. [153] too have reported on the
promoting effect of SO2 in the oxidation of ethyl acetate,
ethanol and propane over a Pt/c-Al2O3 catalyst, and Meyoo
et al. [149] in methane oxidation.
Ojala [3] conducted a short durability test with MnO2–
MgO/Al2O3 catalyst. The catalyst was first used in DMDS
oxidation at its total oxidation temperature (494 C)
continuously for 55 h. After this period, the experiment
was stopped during the night hours. The effect of water
vapor was also tested during the experiments. Water
vapor was introduced into the reaction mixture altogether
for 4 h. In addition, the temperature of the experiment
was decreased to 399 C at the end of the experiment for
3 h. The total aging time was 70 h. MnO2–MgO/Al2O3
catalyst showed excellent stability during the whole aging
period. The activity remained virtually unchanged (con-
version was 100%) from the beginning almost to the end
of the experiment, regardless of the addition of moisture
in the reaction mixture. The conversion was decreased to
*96% when the reaction temperature was decreased to
399 C; 10 C below the T100 temperature. Examination of
the catalyst by XRD after the time-on-stream test showed the
presence of sulphates on the catalyst surface [3].
Ojala [3] also followed the characteristics of different Pt
and Pd-containing catalysts supported on Al2O3 as well as
MnO2–MgO, CuxMg(1-x)Cr2O and CuxCr2O4 before and
after DMDS oxidation by chemisorption (for catalysts 1–4)
and specific surface area (for all catalysts) as well as pore
123
1238 Top Catal (2011) 54:1224–1256

Table 4 Specific surface areas,

Catalyst BET (m2 g-1) Decrease in Metallic surface area (m2 g-1 metal)
decrease in dispersion and
dispersion (%)
metallic surface areas of the Before After Before After
catalysts before and after the
light-off tests Pd/Al2O3–Ce (1) 72 40 87.7 112.2 7.7
Pt/Al2O3 (2) 143 130 up to 100 26.7 down to 0.00
Pt/Al2O3–Ce (3) 65 40 98.0 126.8 2.6
Pt–Pd/Al2O3–Ce (4) 47 25 96.7 90.3 3
MnO2–MgO (5) 171 94 n.d. n.d. n.d.
CuxMg(1-x)Cr2O (6) 105 85 n.d. n.d. n.d.
CuxCr2O4 (7) 102 119 n.d. n.d. n.d.

size distribution measurements (for catalysts 5–7) before
and after the light-off tests. Chemisorption measurements
revealed that the metal dispersions as well as metallic
surface areas of the noble metal catalysts (1–4) decrease
markedly during the light-off experiments in spite of the
fact that the activities did not change significantly between
the repeated experiments (see Table 4). Dispersions and
metallic surface areas of Pt-containing catalysts decrease
more than that of Pd-catalysts, which is consistent with the
results of Jones et al. [136]. Specific surface areas also
decreased, except with catalyst CuxCr2O4. The average
pore sizes of catalysts 5–7 increased during the DMDS
oxidation. The increase was most significant with MnO2–
MgO catalyst. This may indicate blocking of smaller pores
and be the first sign of possible catalyst deactivation even if
the activities of the catalysts between the experiments do
not decrease significantly [3].
Using of nano-gold as a catalytic material is rather new
area of catalysis research. However, gold has been already
reported to be active in several applications including
pollution and emission control technologies, chemical
processing of bulk chemicals and in hydrogen production
as well as in fuel cell applications. It is known that gold
catalysts are very active in low temperature oxidation of
CO and nitrogen containing odorous compounds. Since
1992, gold has been used in odour removal purposes in
Japanese toilets [154]. It has been reported that gold
interacts poorly with sulphur. In fact, among the transition
and noble metals, Au exhibits the lowest reactivity towards
sulphur [155]. Ojala et al. have tested Au catalysts sup-
ported on different types of activated carbon and Al2O3.
They used MM and DMDS as model SVOC compounds
and found very promising results concerning low complete
conversion of tested compounds. However, further research
is needed concerning the catalyst durability and regenera-
tion possibilities [156].
2.2 Structured Catalysts
In previous chapters the catalytic materials in selected
applications were discussed. This chapter will concentrate
Table 5 Different catalyst shapes, typical size and reactor type used
[157]
Shape Size Reactor type
Microspheres d = 20–100 lm Fluid bed reactor, slurry reactor
Spheres d = 1–10 mm Fixed bed reactor, moving bed
reactor
Granules d = 1–20 mm Fixed bed reactor
Beads d = 1–15 mm
Pellets d = 13–15 mm Fixed bed reactor
H = 3–15 mm
Extrudates d = 1–50 mm Fixed bed reactor
more on the structured catalysts, since they are typically
used in industrial applications. Compared to extrudates or
pellets as catalyst supports, honeycomb monoliths show
many advantages: (i) lower pressure drop, (ii) better ther-
mal shock and attrition resistance, (iii) uniform flow dis-
tribution and mass/heat transfer conditions, (iv) shorter
diffusion length, and (v) large heritage from cleaning of car
exhaust gases. The shape forming of catalysts and supports
is a key step in the catalyst preparation procedure. The
shape and size of the catalyst particles should promote
catalytic activity, strengthen the particle resistance to
crushing and abrasion, minimise the bed pressure drop,
lessen fabrication costs and distribute dust build-up uni-
formly. Unfortunately, several of these objectives are
mutually exclusive. For example, small particle size
increases activity, but also increases bed pressure drop.
Thus, the best operational catalysts have the shape and size
that represent an optimum economic trade-off. The choice
of the shape and size is mainly driven by the type of reactor
(Table 5) [157].
Moreover, for a given reactor the best shape and size of
the catalyst particles depend on the hydrodynamics and
heat and mass transfer limitations. It is therefore necessary
that the catalyst exhibits physical strength as well as con-
tinuous catalytic activity. The catalyst is only as good as its
substrate and diverging requirements have to be optimized
to obtain a compromise between hardness and high surface
area. The challenge is to develop a carrier (or substrate)

123
Top Catal (2011) 54:1224–1256
Fig. 3 Different shaped carriers proposed by CTI Company (Salin-
dres, France)
with very good thermal and mechanical properties. Several
research groups have devoted great efforts for years to
develop the shaped catalysts for different applications.
Different forms of carriers have been studied such as
monoliths, foams, pellets and spheres (Fig. 3) [158–160].
The success of cordierite monoliths as catalyst sub-
strates in the treatment of automotive exhaust gases has
given rise to interest in the chemical industry to use
cordierite monoliths as substrates for catalytic reactors.
For many of these applications, the use of several sub-
strate materials and designs can be utilized since the
thermal shock requirements are not as demanding as in
automotive catalysis. In general, many inorganic catalyst
support materials used today in conventional chemical
and refining applications can be extruded into a monolith
form. Monolithic catalysts have become the most diffuse
and economically significant application of catalytic
reaction engineering and industrial catalysis so far [161].
This is due to the commercial success of such well-known
environmental catalysis processes as: (i) the purification
of exhaust gases from automobiles [162, 163], (ii) the
abatement of NOx emitted in the stack gases from power
stations by selective catalytic reduction processes [162,
164], (iii) the catalytic combustion of VOCs [165, 166]
and space propulsion [167]. Their potential for application
in heterogeneous catalysis has also been widely investi-
gated, as reviewed by Cybulski and Moulijn [168].
1239
Further promising large-scale applications are foreseen
in multiphase processes, in which monolithic catalysts
compare favourably to slurry and trickle bed catalysts,
particularly for fast reactions at high temperatures (steam
reforming, partial oxidation of hydrocarbons to synthesis
gas, oxidative dehydrogenation, etc.). Since the catalyst
consists of one piece, no attrition due to moving particles in
a vibrating case occurs. Furthermore, the large, open
frontal area giving access to straight channels results in an
extremely low pressure drop and prevents the accumulation
of dust. Compared to extrudates or pellets as catalyst
supports, honeycomb monoliths show many advantages as
described above. However, monoliths also have some
disadvantages, the major ones being laminar flow through
the channels, lack of interconnectivity between the chan-
nels, and poor radial heat conductivity. A laminar flow
profile yields a large residence time distribution, which is
unfavorable for high conversion levels [169]. Although
radial transport is due to diffusion of fluid phase reactants
inside the porous wash-coat, this transport is sufficiently
fast due to the small channels and high gas diffusivity. On
the contrary, in the liquid phase the diffusivity is three
orders of magnitude lower and this may be one of the
reasons why monoliths are not popular for liquid phase
reactions [157]. Even though monolithic and structured
catalysts are commonly used, very little information is
available so far in the open and scientific literature about
their preparation methods, and probably because most
preparation work is done by industry, and a commercial
interest in publishing the progress achieved is scarce.
In general, two different types of monoliths can be
distinguished: metallic and ceramic monoliths. The thermal
conductance of metallic monolith is much larger and the
amount of solid per unit volume is lower for metallic
monoliths containing a limited amount of metal. As a
result, the heat capacity is very low, which leads to rapid
heating and cooling. Metallic monoliths are produced
exclusively by corrugation, followed by rolling up or
folding into monoliths of the shape and size required.
Metallic monoliths have to withstand oxidizing conditions.
Alloys stable in an oxidizing environment at elevated
temperatures are Ferroalloy, an alloy containing aluminum
(0.5–12%), chromium (20%), yttrium (1–3%), and iron,
and kanthal, an alloy containing aluminum (5.5%), chro-
mium (22%), cobalt (0.5%), and iron [170]. The stability of
these alloys is due to segregation of a dense protecting
layer of alumina on the surface, but, due to the presence of
this alumina layer, welding of the alloys is hardly possible
[170–172]. Ceramic monoliths can be manufactured by
extrusion or by corrugation, the former being the technique
mainly used, and employing various materials. Cordierite
2MgO2Al2O35SiO2, is the most often used catalyst sup-
port material despite the low maximum temperature
123
1240 Top Catal (2011) 54:1224–1256

(1200 C). Mullite is also used for the production of
monoliths, with the composition 3Al2O32SiO2. Zirconia is
suitable for higher temperatures, but the porosity necessary
for good washcoat adhesion can be difficult to achieve.
Silicon carbide, silicon nitride and aluminium titanate are
the other examples of materials that can be used at tem-
peratures exceeding 1200 C. The support is usually an
inert surface that provides a means of spreading out the
metal catalyst for its most effective use. In some cases, the
support may contribute to catalytic activity, depending on
the reaction and reaction conditions. However, the effect of
changing support material was observed to be small,
probably smaller than the effect of catalyst geometry [173,
174]. Table 6 gives information about monolithic materials
used on high temperature catalytic combustion.
Since monolithic carriers possess an inherently low
surface area (typically 0.5–0.7 m2 g-1), the catalytically
active component is present on the monolith walls sup-
ported on a finely divided, high-surface area materials
(called carrier or secondary support so that it is not con-
fused with the ‘‘primary’’ support, the honeycomb). The
preferred procedure to apply the secondary support before
or after loading with the active component is dip-coating
(or wash-coating) and is by far the most used technique for
both metallic and ceramic monoliths [175–177]. It is the
key step for the preparation. Among the various choices for
carrier materials, c-alumina is the most commonly used,
since it can maintain a high surface area at high tempera-
ture range (600–1000 C). Washcoating consists of
depositing an alumina layer of high surface area onto the
surface of the monolithic support: the channels of the
monolith are filled with a slurry or sol of the secondary
support, which is thermally stabilized by addition of, e.g.,
lanthanum oxide or silica [178, 179]. Few papers in the
open literature report about the preparation and studies of
the washcoat properties. The formation of a strong bond
between the support and the active phase is a key factor.
High surface areas are very desirable and favorable to
disperse the active components. The washcoat should also
present a high thermal stability and an excellent adhesion
on honeycomb support. The thixotropy of Al2O3 sol and its
effects on the washcoat loading have been also investi-
gated. The most important factor is the solid content of the
dispersion. The addition of stabilizers, surface-active
agents and acetic acid is able to affect the sol thixotropy.
The influence of rare earths on the thermostability and
surface area of washcoating was studied by Ding et al.
[180]. After secondary coating of the monolith, the active
phase is deposited by the wet impregnation technique.
Finally, the catalysts undergo heat treatment: calcination in
air and/or reduction in hydrogen in the case of noble
metals. As a conclusion, the shaped catalysts are very
interesting and useful in the catalytic oxidation of VOC.
Monoliths and foams present many advantages but require
the deposit of a second support by coating to increase their
specific surface areas. There are several sol–gel processes
which allow the deposition of the gamma alumina, but very
few works concerning the deposition of the other supports

Table 6 Monolith materials for high temperature catalytic combustion [173]

Material Composition Max. temp. (C) Thermal Remarks
expansion

Aluminum titanate Al2TiO5 1800 2

Cordierite Mg2Al4Si5O18 1200–1400 1 Excellent thermal shock resistance,
moderate cost
Dense alumina c-, a-Al2O3 1500–1600 8 Low cost
FeCr alloy 15% Cr, 5% Al, 1250–1350 11 Excellent thermal shock resistance,
Y traces, bal. Fe low cost
Magnesia MgO 1800 10
Mullite Al6Si2O13 1350 2 Good corrosion resistance
Mullite aluminum titanate 1550 4 Good thermal shock resistance
NZP NaZr2(PO4)3 \1500 \2
Silicon carbide SiC 1550–1650 5 Good thermal shock resistance,
low–high cost
Silicon nitride Si3N4 1200–1540 3.7 Good thermal shock resistance,
low–high cost
Spinel MgAl2O4 1400 –
YAG Y3Al5O12 [1400 5.6
Zirconia ZrO2 2200 10 Good thermal shock resistance
Zirconia-spinel – 1700 –
Zirconium mullite – 1550 4

123
Top Catal (2011) 54:1224–1256
such as CeO2, TiO2, and MgO. The challenge thus is to
develop sol–gel procedures that would allow the deposition
of the other supports which would present properties
(acido-basic, redox, high oxygen mobility etc.) that are
interesting for the oxidation of a given pollutant.
3 Catalytic VOC Abatement Technologies
The VOC emissions can be treated in many different ways.
Depending on the quality and quantity of the emissions
either recovery or destruction based methods can be used.
Recovery-based methods such as adsorption, condensation
etc. are suitable when the emission mixture is not very
complicated and the recovered chemicals will have some
economical value either directly to the process from where
they are emitted by re-use or then by selling the recovered
chemicals further. At present VOCs are used in process
industry as solvents, cleaners, lubricants and fuels [181].
Otherwise, destruction based methods prevail. These
methods include biodegradation and incineration either
with or without using a catalyst. Catalytic abatement is
suitable when the emission mixtures are complicated and it
can be applied from small total VOC concentrations to
rather high concentrations.
The development of catalytic incineration technology is
mature. The first examples of catalytic incinerators come in
1940s [78]. The general advantage of catalytic incineration
over thermal combustion is that the energy requirements
are significantly lower while abatement efficiency can be
very high [182]. In the same time, thermal NOx formation
is minimized, since the temperature does not increase close
to 1300 C [135, 183]. Following chapters present in more
detail how the energy-efficiency of catalytic incineration
process can be further improved. It also gives few exam-
ples about the possibilities how to improve catalytic oxi-
dation. Sometimes it is not enough to destroy the original
VOC emissions, but it is important also to take into account
other substances than VOC that may be included in the
emissions. Furthermore, sometimes the oxidation products
are also harmful and need to be further treated. In these
cases hybrid technologies are employed. Finally, a special
possibility of converting the VOC emissions to valuable
chemicals is presented.
3.1 Catalytic Incineration and Heat Recovery
The catalytic incinerator typically consists of several parts.
It includes a filter, catalyst, reactor, preheating system,
instrumentation and controls, analytical equipment, heat
exchangers, pipings and valves etc. [2, 78, 133, 184]. In
addition to these, sometimes further treatment is needed for
formed reaction products. This will be discussed in more
1241
detail later in this paper. The main process variables
affecting the efficiency of catalytic incineration that need
to be taken into account when designing an incinerator are
concentration, composition of emission mixture, particles,
existence of catalyst poisons or masking agents, total flow
and residence time, type of a catalyst, pre-heating need,
oxidation temperature, heat recovery and possible further
treatment of oxidation products [78, 184–186].
The emission flow coming from a process can be already
rather hot, but if not, further pre-heating of the emissions to
the reaction temperature is important. This can be carried
out either using a pre-heat burner [78], but also by using
reaction heat from VOC oxidation and a heat exchanger. It
has been seen that pre-heating of the emission may
improve total oxidation results. The effect may be 5–30%,
which is more than the conversion of VOC during the pre-
heating. This is suggested to arise from the formation of
radicals that contain hydrogen, oxygen, hydroxyls and
organic radicals [187]. This is also an important issue to
keep in mind when designing a catalyst test reactors for
VOC oxidation at the laboratory. Some VOCs are rather
reactive and they may react already without a catalyst and
it has to be taken into account when interpreting the results
of testing the activities of the catalysts. The needed amount
for pre-heating and actual temperature needed in catalytic
oxidation of VOC emission mixture depends strongly on
VOCs to be treated. For solvent emissions, generally
temperatures around 350 C are sufficient in an industrial-
scale treatment, but for CVOCs and SVOCs the tempera-
ture needs to be higher, even up to 500 C [3, 188].
Figure 4 shows the results of catalytic oxidation of several
organic compounds over a Pt catalyst.
The reactivity of the VOC depends on the catalyst
qualities but also on the bond-strengths of the compounds.
The higher the strength of the weakest bond in a molecule
is, the higher the temperature needed for the initiation of
the reaction [189]. Another feature affecting the catalytic
VOC oxidation is the mixture effect of VOCs. It has been
proven that some VOCs inhibit the oxidation of other
VOCs, but also some additive compounds may improve
oxidation or the selectivity of the reaction. Figure 5 shows
an example how the formation of HCl in DCM catalytic
oxidation is affected by water addition. More detailed
examples of mixture-effects and reactivities of the VOCs
are given in Sect. 2.1.
The concentration of the emission mixture affects also
the needed oxidation temperature. Low concentration e.g.
50 ppm may be easily treated, but if very high abatement
efficiency is needed, the heat needed for the oxidation of
the last ppms may be more expensive to produce than to
use a solid adsorbent at the end of the process. High con-
centration e.g. 10,000 ppm will need more residence time
and typically higher temperatures. However, it has been
123
1242 Top Catal (2011) 54:1224–1256

Fig. 4 Catalytic oxidation of 100

hexane, toluene, i-butanol and
acetone over a Pt/Al2O3-catalyst 90

80

70

Conversion (%)
60
hexane
50 toluene

40 ibutanol

acetone
30

20

10

0
0 100 200 300 400 500 600 700
-10
T before catalyst (°C)

Fig. 5 Effect of H2O on the

selectivity of oxidation of DCM
(water 1.5 wt%, GHSV
28,000 h-1, CDM 500 ppm)

seen, that higher concentration may mean higher conver-
sion of VOC when the heating is kept constant. This may
be due to improvement of the production of exothermic
heat of reaction that causes an increase in the temperature
on the surface of the catalyst and therefore improves the
oxidation [186].
Residence time and the amount of the needed catalyst
depend on the total flow of the emissions. Used space
velocity (GHSV, denoted as h-1) depends on the qualities
of the catalyst (activity, selectivity, deactivation) and the
emission stream. The catalytic bed structure used typically
in catalytic incineration is a fixed bed or a monolith. A
fluidized-bed structure could bring certain advantages in
some special cases, since it has the advantage of a very
high mass-transfer rate. It also has higher bed-side heat
transfer coefficient and they are more tolerant to PM. When
pressure drop caused by a catalyst bed is considered, using
a monolithic catalyst is most advantageous [1, 41]. The
amount of the catalyst affects strongly the capital costs of
an incinerator. With a small size of an incinerator the price
of a catalyst is around 3%, but with large capacities it can
be even over 20%.
Since emission limits are quite strict, the high oxidation
temperature should be used to reach high conversion and to
meet the emission limits. However, high temperature
means higher costs for the treatment but also sometimes it
will cause a safety risk. This risk arises from the fact, that
at high concentrations VOC emissions are explosive.
Therefore the temperature of oxidation is limited so, that it
stays always 25% below the lower explosive limit of the
mixture treated [78]. In addition, high temperature may
cause deactivation of the catalyst. Over-heating of the
catalyst may occur if the distribution of a VOC containing
flow is not even and hot spots are formed in certain parts of
the catalytic bed. Other possible situation of over-heating
may occur if the concentration of VOC at the inlet of an
incinerator increases very quickly so that automatic sys-
tems that are used to prevent this kind of situations do not

123
Top Catal (2011) 54:1224–1256
Fig. 6 A Si-deactivated
catalyst (doped Pt/Al2O3)
work fast enough. Currently there exist catalytic incinera-
tors that have been in industrial use for 20 years without
deactivation of the catalyst [190]. In addition, after deac-
tivating the sample catalyst during 25 months in industrial
conditions no signs of major deactivation of the catalysts
was observed [191]. Therefore, it can be said that in solvent
VOC treatment, the deactivation of the noble-metal cata-
lysts is not a major issue. However, the case is different for
example with CVOCs and SVOCs. In addition, the special
case where significant amount of organic or inorganic Si is
present, the special care on the deactivation of the catalyst
should be taken. Figure 6 shows an example of Si-deacti-
vated catalyst. Other possible sources of deactivation of the
catalyst in VOC abatement are for example metals in gas
flow or other compounds that are unknown [192]. It is quite
typical that the full composition of the emissions of a
process is not known and that may bring some surprises
when employing certain abatement technology. In general,
the main deactivation mechanisms in VOC oxidation are
masking or ‘coking’ of the catalyst and poisoning or
inhibition due to non-VOC compounds in a gas stream
[3, 184]. Regeneration of the catalysts can be carried out
even on-site, for example simply by heating the catalyst to
higher temperature to oxidize or vaporize the masking
compounds (e.g. coke) on the catalytic surface. Another
possibility is using the solvent, but typically in these cases
regeneration is not done on-site.
1243
As mentioned before, the energy efficiency of the
abatement process can be improved by using a heat
recovery or exchange. There are two major possibilities for
that, i.e., regenerative heat exchange with flow reversal
(RFR, reverse flow reactor) and recuperative heat
exchange. It can be estimated that the efficiency of the heat
recovery in the case of regenerative heat exchange is 95%
and in the case of recuperative heat exchange 75%. The
efficiency of the thermal recovery system depends on the
process operating characteristics [193]. The recovered heat
is typically used in the heating of the incoming VOC
emission flow, but it can in some cases be used in the
preceding process. It can also be used to produce steam or
hot water in a waste heat boiler and to heat the endothermic
reaction such as methane steam reforming in the coupled
reactor [78, 194]. When the produced heat is used in
heating the incoming gas, the incinerator may achieve
autothermal operation which means that no extra heating is
needed to maintain process operation.
In regenerative heat exchange related to VOC oxidation
two heat recovering blocks are used that are placed so in
the both sides of a catalyst that one block is cooling and
releasing the heat to the reacting VOC emission before the
catalyst while the other is storing the exothermal reaction
heat after the catalyst. At certain point of time or temper-
ature flow is then reversed and the heating–cooling cycle is
repeated again. In recuperative heat exchange, the cold
123
1244
VOC emission stream is flowing on the other side of a wall
(a plate or other construction) separating the cold and the
hot gas streams from each other. The exothermic reaction
heat is conducting through the plate to heat-up the
incoming VOC emission. A regenerative system provides
extremely high thermal energy recovery and even low
VOC concentrations can be treated in self-sustaining mode
without extra fuel. It has been reported in the case of flow
reversal reactors that the reversing the flow also improves
the oxidation efficiency of the process [195–197]. This may
be due to a self-cleaning property of the reverse flow
reactors where accumulated particulate materials are
released when the flow direction changes and also due to
the varying reaction zone inside the catalyst bed with
varying thermal and flow conditions. A main disadvantage
of the regenerative heat exchangers is that a small fraction
of exhaust gases will pass the process as un-reacted. This
has been minimized by using optimized control and in
some cases more complicated valve systems [198, 199].
Regenerative systems consist of pneumatically or electri-
cally driven valves and control system that give more
capital investment and maintenance compared with the
recuperative system. These drawbacks are in most appli-
cations still covered by lower energy consumption. Rela-
tively low and steady VOC concentrations have a good and
proven potential for achieving autothermal operation con-
ditions in regenerative heat exchange-case. A recuperative
heat exchange system is easier to operate in the cases
where the flow rate and VOC content varies a lot. In
addition, recuperative systems generally are smaller and
lighter in weight compared with regenerative heat recovery
systems. Thus, recuperative systems have shorter period to
reach operation conditions compared to regenerative sys-
tems. The recuperative systems have advantages especially
treating higher concentrations or when the leakage of any
fraction of VOCs is not allowed. In the last decade reverse
flow reactors (regenerative heat exchange) have taken the
advantage over recuperative systems that were first applied.
However, both heat exchange types have found their own
application areas.
3.2 Emerging Technologies
This chapter will give a few examples on non-conventional
catalytic oxidation. In these examples different kinds of
activation of the catalysts are used, namely, light, plasma
and microwaves.
3.2.1 Photocatalysis in VOC Oxidation
Photocatalysis is a process that uses UV-light in the acti-
vation of the catalysts that are usually semiconductors such
as metal oxides or sulfides [200]. Photocatalysis has been
123
Top Catal (2011) 54:1224–1256
applied to water purification purposes for several years, but
rather recently the research activities on utilization of
photocatalysis in air treatment have increased. Photoca-
talysis involves two simultaneous reactions that are oxi-
dation from photogenerated holes and reduction from
photogenerated electrons. This process needs to be bal-
anced in order to retain the photocatalyst unchanged [200].
Probably the most known photocatalyst is titanium
dioxide, since its photocatalytic effects have been studied
already in 1930s [201]. In decomposition of gaseous pol-
lutants, if there is a sufficient supply of O2 and UV illu-
mination, VOCs can be completely oxidized to CO2, H2O
and mineral acids on a TiO2 thin film. The decomposition
rate is influenced by e.g. light intensity, substrate concen-
tration, O2 partial pressure, humidity, substrate type, etc. In
addition, photocatalysts may be deactivated by the reaction
intermediates that block the active sites [200]. Photocata-
lytic VOC oxidation can be carried out over various dif-
ferent TiO2 systems. For example mesoporous films of
TiO2 and optical fibers are highly promising photocatalysts
for the photocatalytic oxidation of gaseous pollutants. TiO2
coated on textile is a useful catalytic material in VOCs
photocatalytic degradation as well. Also TiO2 mixed with
cementitious materials like Portlant cement have been
designed and tested in the same purposes. Fe-modification
of photocatalysts seems to enhance decomposition of dif-
ferent hydrocarbons in air [202].
Zuo et al. have tested photocatalytic degradation of
several VOCs. They reported that reactivity of the tested
VOCs in photocatalysis followed the order: TCE [ chlo-
roform [ toluene [ DCM [ benzene [ carbon tetrachlo-
ride. They also tested a series of modified TiO2 catalysts
and found out that SnO2/TiO2 was very active in benzene
degradation and that mineralization rate over Fe3?/TiO2
was the highest among the tested catalysts [203]. Akly
et al. have tested silica–titania composites in photocatalytic
removal of gas-phase toluene. They found out that con-
version of toluene increased almost by 60% when the rel-
ative humidity was increased from 13% to 90%. The best
conversion they achieved in the experiments was 93%
[204]. Another example on VOC oxidation is a study by
Benoit-Marquié et al. [205] where a TiO2 catalyst was used
in the photocatalytic treatment of 1-butanol and 1-butyl-
amine. They found out that from the tested compounds
1-butanol was easier to degrade. In addition, no deactiva-
tion was observed during 50 h of testing time.
The practical use of photocatalysis is not as extensive as
the scientific research of the field would presume. Paz
made a patent overview on TiO2 photocatalysis in air
treatment in 2010 [201]. He found out that even if the
number of scientific publications on photocatalysis in water
treatment is significantly higher than publications con-
cerning air treatment, the number of relevant patents is
Top Catal (2011) 54:1224–1256
higher for air treatment. In addition, commercialization of
photocatalytic indoor air treatment is more developed than
that of outdoor air treatment [201]. For example TiO2 is
used to decontaminate, deodorize and disinfect the indoor
air. In addition to low-concentration VOCs abatement
photocatalysis can be used to kill pathogenic microorgan-
isms e.g. bacteria and viruses present in indoor air or sur-
faces [200, 206].
3.2.2 Plasmacatalysis in VOC Oxidation
The combination of non-thermal plasma and catalysis has
also been tested in VOC oxidation. The main reason for
this combination is that certain advantages can be foreseen
when these two technologies are combined. For example, a
catalyst improves e.g. the selectivity of non-thermal plasma
process, but also improve the final conversions of the
reactants. Placing of a catalyst in the discharge zone of a
plasma reactor may affect plasma by changing the dis-
charge type and shifting the distribution of accelerated
electrons as well as by generating new reactive species.
The plasma can affect catalyst properties, adsorption pro-
cess and thermal activation [207–209].
Non-thermal plasma consists of electrons that are
accelerated by an electric field. This will create electrons
that may have temperature up to *250,000 C [207]. This
can further give gas temperatures of several hundreds of
degrees [209]. These electrons are not in thermal equilib-
rium with molecules around and their collisions produce
excited gas molecules. These molecules, when relaxed,
emit photons or heat. The dissociative electron attachment
process creates ions and radicals. These three processes
create a very reactive environment. However, despite of
highly reactive environment, the drawbacks of non-thermal
plasma process are high by-product formation, low min-
eralisation and energy inefficiency [207–209]. In a com-
bined process, catalysts can be placed in principle in two
places; either to the plasma-discharge zone or to location
directly after plasma. The catalyst can be coated on reactor
walls or electrodes; it can be placed in a reactor system as a
packed-bed (shaped catalysts) or as a non-packed catalyst
layer. According to Van Durme et al. [207] the main
attention during the past years has been concentrating on
reactor concepts where the catalyst is placed into the dis-
charge zone.
In VOC oxidation it has been reported that plasma could
be especially effective in the case of chlorinated com-
pounds due to creation of chlorine radicals. These radicals
are formed when Cl-atoms are detached from the molecule,
and after being formed, they are able to initiate chain
reactions [207]. Magureanu et al. [209] have tested several
catalysts based on Mn-phosphates in toluene oxidation.
They used a dielectric barrier discharge at atmospheric
1245
pressure. The catalyst was placed downstream of the
plasma reactor in an oven operating at 400 C. They
observed a synergetic effect already at 100 C, where a
catalyst is not yet active. In general, the best tested catalyst
was Mn-SAPO that resulted in an increase in toluene
conversion, and more importantly, shift towards complete
oxidation products. They believe that the results can be
further improved when a catalyst is placed in the discharge
zone [209]. Futamura et al. [210] have tested BaTiO3 and
MnO2 in a ferroelectric packed-bed reactor and a silent
discharge plasma reactor in VOC abatement. They found
out that BaTiO3 is not improving the reaction whereas
MnO2 is. Close to the complete conversion of benzene was
achieved in the experiments. They tested altogether 10
different chemicals containing chlorinated and brominated
compounds, benzene and CO [210]. Harling et al. [211]
compared one- and two-stage systems in benzene and tol-
uene oxidation over TiO2 and c-Al2O3 supported Ag cat-
alysts. They found out that one-stage system improved the
conversion of both reactants. In toluene oxidation c-Al2O3
and Ag/c-Al2O3 are more active than TiO2 catalysts. They
found almost no effect when Ag was added to c-Al2O3
compared to the situation where it was used alone. How-
ever c-Al2O3 was remarkably better than TiO2 and Ag/
TiO2. Of the chemicals, toluene was more easily oxidized
since it is less-stabile than benzene [211].
Other catalysts and supports tested in plasma catalysis
include noble metals, Ni, Fe2O3, CuO, MnO2, CeO2 and
zeolites. The VOCs oxidized with the plasma catalytic
process have been mainly hazardous chlorinated, fluorated,
brominated compounds, toluene and formaldehyde. In
addition to conventional catalysis, plasma can be used also
to trigger photocatalytic processes [207]. Acceleration of
air purification by combining photocatalysis and electric
discharges has overcome the problem of limited photo-
catalytic oxidation rate [212]. The presence of oxidizers
like O3 and gaseous H2O2 is also needed to enhance the
reaction rate. The increase in the oxidation rate is caused
by partial oxidation of organic compounds in discharge due
to oxygen atoms of ozone and stronger adsorption of these
products on photocatalysts as well as oxidation over TiO2
with ozone [213].
3.2.3 Microwave Process for VOC Oxidation
Catalytic incineration of malodorous SVOCs can be
expensive if the concentration of an emission stream is too
low to maintain autothermal operation. Also, due to very
low odor threshold limits very small (ppb) levels of con-
centration needs to be achieved to make the emission gas
non-odorous. In this kind of a case a non-isothermal
microwave-assisted (mw) catalytic process would be of
interest [214]. Using of mw radiation in heating of
123
1246
chemical reactions has been of interest during recent years
[215–219]. Mw irradiation has been tested also in TCE
abatement. For example, Takashima et al. [218] have tested
mw assisted VOC decomposition, where decomposition is
carried out in the presence of hydrogen. They tested Pt and
Ni catalysts on TCE abatement and found out that the
dechlorination reaction needs an optimum between film
thickness of a catalyst on a support and mw-power supply,
since lower temperatures do not activate the catalyst while
too high temperature causes carbon deposition.
Mw-assisted process described by Kucherov et al. [215]
works in principle so, that on one phase of operation the
VOCs are adsorbed on the catalyst and in the second phase
low-power (\50 W) microwaves are introduced to the
catalyst. Mw irradiation creates selective heating of
metallic particles and thus adsorbed VOCs are oxidized.
This adsorptive-catalytic approach looks attractive from
the theoretical point of view, but it still waits a detailed
experimental study. Another possibility to use mw irradi-
ation in VOC abatement it is to combine it with photoca-
talysis. This kind of operation was presented e.g. by
Horikoshi and Serpone [220]. Their research showed that
acetaldehyde degradation when it was present in humidi-
fied air was up to 90% when the experiment was carried out
over a TiO2 catalyst during 20 min. In this case degrada-
tion was carried out using the UV light emanating from a
microwave-activated microwave discharge electrodless
lamp (MDEL) device. Ighigeanu et al. [217] have proposed
a new hybrid technique for VOC abatement that is based on
combination of electron beams, microwaves and catalysts.
In the process electron beams and microwaves were used to
produce non-thermal plasmas. They used V2O5 as the
catalyst and toluene or toluene-hexane mixture in air as the
reactants and achieved over 90% conversions of VOC in
both cases.
One interesting catalytic material that could be used in
mw-assisted catalytic process is gold nanoparticles, since
they preserve the metallic phase (Au0) in oxidative atmo-
sphere. Metallic form of catalytically active phase is
important since the corresponding oxides may be ‘invisi-
ble’ to mw irradiation. For this reason the catalyst support
material that would work as ‘the main adsorbent’ is cold
while Au0 microcrystals from hot spots when mw irradia-
tion is applied. Kucherov et al. [215] have also tested
HZSM-5 zeolite-supported Au–Rh bi-metallic systems in
methanol-DMDS removal. This bimetallic catalyst seems
to exhibit high activity and stability at 320 C during 8 h of
use. XRD analysis showed that the metallic state was
preserved and the absence of coke was shown by TPO.
This material was suggested to be an attractive in non-
isothermal mw-operation.
Carbon materials interact strongly with mw-heating and
as certain carbons, such as graphite, have a high thermal
123
Top Catal (2011) 54:1224–1256
conductivity they could be used in the applications which
involve high temperatures and with such an organic com-
pounds that do not heat up sufficiently with mw heating
[216]. In this kind of cases carbon materials could be used
to intensify the mw-assisted process.
Another interesting aspect from the engineering point of
view concerning the ‘cold catalysis’ is that the construction
material durability would not be so problematic than usu-
ally in the case of acidic reaction products. There exist
several material possibilities that are durable in acidic
conditions but cannot be used in the case of high temper-
ature. This technology is under development and by now
commercial installations do not exist. Mw irradiation could
also be used in regeneration of catalysts as it is used in
regeneration of adsorbents [221].
3.3 Hybrid Technologies for VOC Abatement
Catalytic oxidation of VOC emissions is not always
enough. Very often different treatment units have to be
combined with the oxidation treatment to either modify the
original emission stream or further treat the oxidation
products. Quite usually some kind of pre-filtration of the
emission stream is needed before the catalytic treatment
unit to remove particulates from the gas flow. Particulates
may cause blocking of heat exchangers and catalyst bed,
but they may also cause deactivation of the catalyst by
masking the catalytic surfaces before it impedes physically
the gas flow. Pre-filtration is very important for example in
the cases where catalytic incineration is used in the treat-
ment of polluted ground. In this kind of applications
powerful pumps are first used to evacuate the VOCs from
the ground. Then VOCs are conducted via pipelines to the
filter and the abatement unit. These kinds of systems are
used for example in the treatment of ground of the old
gasoline station areas. In addition to solid filtration some-
times moisture condensation before catalytic treatment will
increase the energy efficiency of the treatment unit but also
it will reduce pressures concerning possible catalyst hydro-
thermal deactivation. It has been shown that noble metal
catalysts can be affected in the presence of moisture
starting at temperature of 700 C [222].
Oxidations of chlorinated and sulphur-containing com-
pounds produce the compounds that are still harmful. For
example reaction products of CVOCs contain HCl and Cl2.
These two acidic substances that are also very corrosive
need to be further treated. The treatment of these com-
pounds is industrially well-established scrubbing. In this
process the gases are washed with NaOH solution. After
the washing-phase the pH of the washing liquid is adjusted
and then it can be conducted e.g. to the municipal waste-
water treatment plant. Oxidation of SVOCs produces
emissions of SO2. SO2 can be further treated in a similar
Top Catal (2011) 54:1224–1256
way then HCl and Cl2. Quite often the industry that emits
SVOCs in certain phase of the process needs also the
treatment of SO2 in another phase of the process. Then the
outlet gas of catalytic oxidation could be easily connected
to the existing SO2 treatment unit.
During the past few years the reductions of CO2 emis-
sions have been under significant interest of the public and
authorities. Oxidation of VOC is always producing the
emissions of CO2 as well. However, the global warming
potential (GWP) of VOCs are multifold compared to the
CO2 GWP. Therefore it is true, that even if the oxidation of
VOCs is producing CO2 the effect to the global warming is
less than in the case when VOCs are released directly to the
atmosphere. Even so, the storage or utilization of CO2
could be interesting. CO2 can be utilized for example in a
pulp and paper mills in pulp washing-hase [223], to pro-
duce precipitated calcium caronate (PCC) [224], to control
pH [223, 224], and in separation of tall oil [225]. Unfor-
tunately in many CO2 utilization cases CO2 is again
released in air. In the cases of separation of tall oil and in
controlling of pH CO2 is used to replace H2SO4 and
thereby it will reduce mills sulphur loading [225, 226].
3.4 From VOC Emissions to Valuable Chemicals
The idea presented in this chapter is industrially very
tempting. Changing of the emissions to the valuable
chemicals by catalytic treatment instead of destroying them
could give some extra financial profit to the industry
instead of increasing the costs due to installation of the
abatement system. In certain cases this is possible. The
next chapter gives a case-example on using methanol and
methyl mercaptan emissions to produce formaldehyde.
3.4.1 Case: Methanol and Methyl Mercaptan Oxidation
to Formaldehyde
In kraft pulp mills VOCs are formed during the cooking
process of wood. As mentioned by Burgess et al. [227]
methanol is the largest single element of total VOC emis-
sions originating from Kraft pulp mills. The methanol
containing waste gas stream contains also terpenic com-
pounds, H2S, MM, dimethyl sulfide (DMS) and dimethyl
disulfide (DMDS) [133]. One problem related to these
VOC emissions in Kraft pulp mills is that compounds are
soluble in water and increase the biochemical oxygen
demand. In addition to that these very odorous emissions
can be released into the atmosphere from different parts of
the pulping process [133, 228].
Steam stripping of this emission stream, collected from
digesters, evaporators and other process locations, followed
by incineration has been traditionally used to treat these
emissions. In some cases also treatment in biotreatment
1247
bonds is used. Aerobic microorganisms use the methanol as
a carbon source and convert it to carbon dioxide and water
[229, 230]. In steam stripping the foul condensates are
segregated to minimize the total volume of the condensate
which needs to be treated and to minimize the needed
steam consumption in the stripper unit [227, 229, 231,
232]. Even though the treatment of this waste gas stream is
heading to gain good results and recover the fuel value
present in the stream, also problems may occur during
incineration [227, 230]. Methanol containing streams are
changing from time to time and due to changes in the fuel
value of the stream there is a risk of operational upsets in
the boiler or in the lime kiln. Also operational problems of
the lime kiln or the boiler would lead to situation where
also the operation of the steam stripper must be discon-
tinued because there is no place to lead the SOG stripper
overhead gas [230].
The environmental problems related to steam stripping
of methanol containing waste gas stream gives space to a
new thinking and in today’s world also economical aspects
need to be taken into account in every situation. As gen-
erally known pure methanol can be oxidized to formalde-
hyde by using several different catalysts. Being able to
convert the kraft pulp mill waste gas stream containing
methanol to formaldehyde would bring environmental but
also economical benefits to the mills [227, 233].
The commercial formaldehyde process uses methanol
and air as the feed mixture, and either silver or metal
oxides (V2O5, Fe, Mo) as catalysts to intensify the reaction
[234]. In the research field different molybdenum [235–
238] and vanadia based catalysts [239–247] have been
widely under investigation for methanol oxidation. Ai
[235] has studied the performance of V2O5–MoO3 catalyst
in methanol oxidation and has revealed that the V2O5–
MoO3 catalyst is as active as the MoO3–SnO2 catalyst to
produce formaldehyde and more active than MoO3–TiO2
and MoO3–FeO3 catalysts. Mann and Dosi [236] have
gained the maximum yield of formaldehyde at 466 C and
more than 99% conversion with the V2O5–MoO3 catalyst.
Kijenski et al. [239] have reported very high selectivity to
formaldehyde with V2O5/SiO2 and pure silica being inac-
tive. The same authors also present that pure titania per-
formed better than Al2O3, SiO2, MgO as carriers. The
V2O5/TiO2 catalyst has shown out to result in highest
selectivity according to Deo and Wachs [241] and the
oxidation activity increased as a function of vanadium
oxide loading.
TRS emissions, especially methyl mercaptan MM, can
also be used as a feed component in formaldehyde pro-
duction. Mercaptans, such as methyl mercaptan, DMS and
DMDS can be oxidized to formaldehyde with vanadia on
titania and silica catalysts [248, 249]. Ross and Sood [138]
have examined the catalytic oxidation of methyl mercaptan
123
1248
over cobalt molybdate. Sahle-Demessie and Devulapelli
[250] have investigated the oxidation of DMS with ozone
over a V2O5/TiO2 catalyst. Also Al2O3-supported mixed-
metal oxides have been investigated in the oxidation of
DMDS (CH3)2S2 [143].
As mentioned methanol containing waste gas stream
from the pulp mills is contaminated with reduced sulphur
compounds. The catalyst used in commercial formalde-
hyde process cannot be used to oxidize this stream
because the catalysts would deactivate in the presence of
sulphur and deteriorate in the presence of steam [227].
Previously the suitability of V2O5/TiO2 catalyst to oxidize
gas stream from Kraft pulp mill containing methanol and
reduced sulphur compounds has been investigated [230,
248, 250].
Koivikko et al. [251] have investigated the activity of
three different vanadia and titania based catalysts to oxi-
dize methanol and methyl mercaptan separately and in a
mixture to produce formaldehyde. Catalysts used in the
experimental work were TiO2 (Ti), V2O5/SiO2 (VSi) and
V2O5/SiO2 ? 10% TiO2 (VSiTi). These catalysts were
selected for this study because they are expected to be
resistant to fouling of the catalyst in the presence of sulphur
in the gas stream. Two supports, pure SiO2 and [90%
SiO2 ? 10% TiO2], were prepared by acid-catalyzed
hydrolysis of pure tetraethoxysilane or the mixture of tet-
raethoxysilane with a calculated amount of tetrabutoxy
titanium. Supported catalysts containing 3 wt% of V2O5
were prepared by repeated, triple incipient wetness
impregnation of supports by water solution of ammonium
vanadate (chemically pure grade), with intermediate drying
at room temperature and final calcination at 480 C for 2 h.
Catalytic activity measurements were carried out in a
continuous flow fixed-bed reactor at atmospheric pressure.
Details of the experimental set-up and procedure are pre-
sented in the paper of Koivikko et al. [251]. Methanol was
fed by a syringe pump to a vaporizer and mixed with
controlled amount of air. Methyl mercaptan gas was fed
through a mass flow controller and similarly mixed with
air. The total gas flow through the reactor was maintained
at 1 dm3 min-1 giving GHSV of *94,000 h-1. The cata-
lyst bed was fixed in the middle of the reactor tube between
glass wool plugs and the temperature was measured prior
to the catalyst bed. The outlet gas flow was analyzed by
using the Gasmet FTIR gas analyzer Dx-4000 with the
peltier-cooled mercury-cadmium-telluride (MCT) detector
and resolution of 8 cm-1 with 50 scans co-added. The
experimental variables used in the catalyst testing were
catalyst type, catalyst amount in the reactor (10 mg and
100 mg), feed concentration of methanol (1000 ppm),
methyl mercaptan (1000 ppm) and the mixture of methanol
(500 ppm) and methyl mercaptan (500 ppm) and temper-
ature (300 C and 500 C).
123
Top Catal (2011) 54:1224–1256
According to the results of Koivikko et al. [251] a VSiTi
catalyst was the most active catalyst of the three tested
catalysts to produce formaldehyde at temperatures higher
than 300 C. In methanol oxidation reactions only CO2 and
CO were detected besides formaldehyde which indicates
that at temperatures lower than 500 C formaldehyde
production prevails over total oxidation of methanol. CO2
and CO, DMDS and SO2 were formed in methyl mercaptan
oxidation reactions. Other detected reaction products were
sulphur dioxide SO2, DMDS, CO2 and CO when feeding
both methanol and methyl mercaptan together. In methyl
mercaptan oxidation the catalyst loading has a greater
impact on formaldehyde formation compared to methanol
oxidation. For example when raising the catalyst amount
from 10 to 100 mg, the formaldehyde concentration raised
280 ppm with the VSiTi catalyst in methyl mercaptan
oxidation. In methanol oxidation formaldehyde concen-
tration raised only 70 ppm. The results of methanol oxi-
dation with 100 mg of the VSiTi catalyst are shown in
Fig. 7. In the experiments 1000 ppm feed was used and the
reaction temperature was raised from room temperature to
500 C. Figure 7 shows that the optimal temperature for
the formation of formaldehyde over the VSiTi catalyst is
approximately 340 C (75% yield). With the Ti catalyst,
the formaldehyde yield raises up to 65% (524 C), and with
a VSi catalyst to 67% (475 C) during the tests, respec-
tively. Thus, the activity of the catalysts follows the trend
VSiTi [ VSi [ Ti. After the VSiTi catalyst reaches the
optimal temperature, the product concentration starts to
decrease and formaldehyde starts to react further to CO and
again to CO2. Similar results are presented by several
authors [230, 242].
The results of the oxidation of methyl mercaptan with
the VSiTi catalyst are shown in Fig. 8 when the catalyst
loading of 100 mg was used. As in the case of methanol,
the VSiTi catalyst was the most active and the rate of
reaction is highest. With the VSiTi catalyst the maximum
formaldehyde yield (82%) was reached at the temperature
of 430 C. The Ti catalyst was slightly more active than the
Fig. 7 Methanol (1000 ppm) conversion and formaldehyde yield
over 100 mg V2O5/SiO2 ? TiO2 catalyst
Top Catal (2011) 54:1224–1256
Fig. 8 Methyl mercaptan (1000 ppm) conversion and formaldehyde
yield over 100 mg V2O5/SiO2 ? TiO2 catalyst
Fig. 9 Feed conversion (500 ppm methanol ? 500 ppm methyl
mercaptan) and formaldehyde yield over 100 mg V2O5/SiO2 ? TiO2
catalyst
VSi catalyst in the selective oxidation. The results of the
oxidation of a methanol and methyl mercaptan mixture to
produce formaldehyde are presented in Fig. 9. A catalyst
loading of 100 mg was used and the used feed concentra-
tion was 500 ppm for both methanol and methyl mercaptan
so that the total concentration of the reactants was
1000 ppm. The tests showed that the VSiTi catalyst has an
optimal temperature at around 410 C (880 ppm/413 C).
Both of the feed compounds are reacting completely over
the VSiTi catalyst and the other two catalysts give good
results as well. Maximum formaldehyde yield gained with
100 mg of Ti was 85% (500 C) and with 100 mg of VSi
61% (480 C). The highest formaldehyde yield was gained
when feeding the mixture of methanol and methyl mer-
captan [251].
4 Conclusions and Research Needs
Even if the catalytic oxidation of VOCs has been used for
several years, and it has been proven a feasible VOC
abatement technology, certain improvements are needed.
During the years the economy of the process has improved
1249
e.g. when heat recovery was introduced to the process and
when several different catalytic materials have been devel-
oped and tested. Continuously tightening VOC emission
regulations are bringing new challenges to the effectiveness
of the current installations, but also new application areas for
catalytic abatement. Due to this, new innovations are needed
in designing of new more durable and selective catalysts and
in the development of the current technology. Changing
towards hybrid systems, further reduction the operating
costs and making profit from the emissions by changing the
wastes to valuable products are bringing new possibilities to
researchers. Due to tightening regulations also the gas
measurement systems should be developed further to for
example ensure the efficiencies of the abatement units.
Acknowledgments The authors wish to thank everybody related to
the research presented in this paper. Especially the work of Mr. Jorma
Penttinen and M.Sc. Florence Large are appreciated. The Academy of
Finland is acknowledged for the financial contribution.
References
1. Hayes RE, Kolackowski ST (1997) Introduction to catalytic
combustion. B.V. Published, Amsterdam
2. Moretti EC (2001) Practical solutions for reducing volatile
organic compounds and hazardous air pollutants. AIChE, New
York
3. Ojala S (2005) Catalytic oxidation of volatile organic com-
pounds and malodorous organic compounds. PhD thesis, Uni-
versity of Oulu, Oulu. ISBN 951-42-7870-4 (PDF), http://herk
ules.oulu.fi/isbn9514278704/isbn9514278704.pdf. Accessed 26
Aug 2011
4. Council Directive 1999/13/EC of 11 March 1999 on the limi-
tation of emissions of volatile organic compounds due to the use
of organic solvents in certain activities and installations (1999)
Off J Eur Union. http://eur-lex.europa.eu/LexUriServ/LexUri
Serv.do?uri=OJ:L:1999:085:0001:0022:EN:PDF. Accessed 26
Aug 2011
5. European Environment Agency (2010) European Union emis-
sion inventory report 1990–2008 under the UNECE convention
on long-range transboundary air pollution (LRTAP). EEA,
Copenhagen
6. Directive 2004/42/CE of the European Parliament and the
Council of 21 April 2004 on the limitation of emissions of
volatile organic compounds due to the use of organic solvents in
certain paints and varnishes and vehicle refinishing products and
amending Directive 1999/13/EC (2004) Off J Eur Communities.
http://eur-lex.europa.eu/LexUriServ/LexUriServ.do?uri=OJ:L:
2004:143:0087:0096:EN:PDF. Accessed 26 Aug 2011
7. Commission decision of 3 September 2002 establishing revised
ecological criteria for the award of the community eco-label to
indoor paints and varnishes and amending decision 1999/10/EC
(2002) Off J Eur Communities. http://eur-lex.europa.eu/Lex
UriServ/LexUriServ.do?uri=OJ:L:2002:236:0004:0009:EN:PDF.
Accessed 26 Aug 2011
8. Directive 2001/81/EC of the European Parliament and of the
Council of 23 October 2001 on national emission ceilings for
certain atmospheric pollutants (2001) J Eur Communities. http://
eur-lex.europa.eu/LexUriServ/LexUriServ.do?uri=OJ:L:2001:
309:0022:0030:EN:PDF. Accessed 26 Aug 2011
123
1250
9. Ordinance on incentive taxes on volatile organic compounds
(VOCV) http://www.admin.ch/ch/d/sr/8/814.018.de.pdf. Acces-
sed 26 Aug 2011
10. United States Environmental Protecting Agency. Definition of
volatile organic compounds (VOC) as of 3/31/2009 40 CFR
51.100(s) definition volatile organic compounds (VOC). http://
www.epa.gov/ttn/naaqs/ozone/ozonetech/def_voc.htm. Accessed
26 Aug 2011
11. United Nations Economic Commission for Europe. Protocol to
the 1979 convention on long-range transboundary air pollution
to abate acidification, eutrophication and ground-level ozone.
http://live.unece.org/env/lrtap/multi_h1.html
12. Environment Canada (2010) Volatile organic compound defi-
nition. http://www.ec.gc.ca/cov-voc/default.asp?lang=En&n=10
5A29F5-1. Accessed 17 Mar 2010
13. Protection of the Environment Operations (Clean Air) Regula-
tion (2010) New South Wales Government, NSW Legislation.
Parliamentary Counsel’s Office. http://www.legislation.nsw.
gov.au/maintop/view/inforce/subordleg?428?2010?cd?0?N.
Accessed 26 Aug 2011
14. Directive 2008/50/EC of the European Parliament and of the
Council of 21 May 2008 on ambient air quality and cleaner air
for Europe (2008) Off J Eur Union. http://eur-lex.eu
ropa.eu/LexUriServ/LexUriServ.do?uri=OJ:L:2008:152:0001:00
44:EN:PDF. Accessed 26 Aug 2011
15. European Commission, Environment. http://ec.europa.eu/envir
onment/air/pollutants/stationary/index.htm. Accessed 26 Aug
2011
16. Air quality standards, Australian Government Department of the
Environment, Water, Heritage and the Arts. http://www.enviro
nment.gov.au/atmosphere/airquality/standards.html#emission.
Accessed 26 Aug 2011
17. Protection of the Environment Operations (Clean Air) Regula-
tion (2010) Australasian Legal Information Institute, New South
Wales Consolidated Regulations. http://www.austlii.edu.au/au/
legis/nsw/consol_reg/poteoar2010601/. Accessed 26 Aug 2011
18. Summary of Clean Air Act, United States Environmental Pro-
tection Agency, 42 U.S.C. §7401 et seq. (1970) http://www.epa.
gov/lawsregs/laws/caa.html. Accessed 26 Aug 2011
19. The Clean Air Act as Amended Through P.L. 108–201, Feb-
ruary 24, 2004. United States Senate Committee on Environ-
ment and Public Works. http://epw.senate.gov/envlaws/cleanair.
pdf. Accessed 26 Aug 2011
20. $$$ for Clean Engine Project. California Environmental Pro-
tection Agency, Air Resources Board. http://www.arb.ca.gov.
Accessed 26 Aug 2011
21. Ambient Air Quality Standards. California Environmental Pro-
tection Agency. Air Resources Board (08/03/10). http://www.
arb.ca.gov/research/aaqs/aaqs2.pdf. Accessed 26 Aug 2011
22. Canadian Environmental Protection Act, 1999, Published by the
Minister of Justice. http://laws-lois.justice.gc.ca, http://laws.jus
tice.gc.ca/PDF/Statute/C/C-15.31.pdf. Accessed 26 Aug 2011
23. Volatile organic compound (VOC) concentration limits for
architectural coatings regulations (SOR/2009-264). Canada
Gazette Part II, 143(20). http://canadagazette.gc.ca/rp-pr/p2/2009/
2009-09-30/pdf/g2-14320.pdf#page=73. Accessed 26 Aug 2011
24. Volatile organic compound (VOC) concentration limits for
automotive refinishing products regulations (SOR/2009-197),
Canada Gazette Part II, 143(14). http://canadagazette.gc.ca/rp-
pr/p2/2009/2009-07-08/pdf/g2-14314.pdf#page=200. Accessed
26 Aug 2011
25. Textes Juridiques. Departement de l’Environnement, Royaume
de Maroc. http://www.minenv.gov.ma/2_cadre_juridique/air.
htm. Accessed 26 Aug 2011
26. Department of Environmental Affairs, Republic of South Africa.
http://www.environment.gov.za/. Accessed 26 Aug 2011
123
Top Catal (2011) 54:1224–1256
27. National Environmental Management: Air Quality Act 39 of
2004. http://www.environment.gov.za//PolLeg/Legislation/2010
Mar31/AIR%20QUALITY%20ACT,%202004.doc. Accessed
26 Aug 2011
28. National Ambient Air Quality Standards. Government Gazette
No. 32816 24 December 2009, Republic of South Africa. http://
www.environment.gov.za//PolLeg/Legislation/2010Mar31_1/AIR
%20QUALITY%20STANDARDS.pdf. Accessed 26 Aug 2011
29. Improving air quality, Department of Environmental Affairs,
Republic of South Africa. http://soer.deat.gov.za/170.html#1458
. Accessed 26 Aug 2011
30. Clean Air Conservation Act. Ministry of Environment, Republic
of Korea. http://eng.me.go.kr/file.do?method=fileDownloader
&attachSeq=972. Accessed 26 Aug 2011
31. Enforcement Decree of the Clean Air Conservation Act. Min-
istry of Environment, Republic of Korea. http://eng.me.go.kr/
file.do?method=fileDownloader&attachSeq=977. Accessed 26
Aug 2011
32. Cleaning China’s air: first regional air quality regulations. The
network for climate and energy information. http://www.china
faqs.org/blog-posts/cleaning-chinas-air-first-regional-air-quality-
regulations. Accessed 26 Aug 2011
33. The gateway to environmental law, Ecolex. http://www.
ecolex.org/ecolex/ledge/view/RecordDetails;document_Mercha
nt%20Shipping%20%28Prevention%20of%20Air%20Pollution
%29%20Regulation%20%28Chapter%20413M%29..html?DID
PFDSIjsessionid=3F7456CFFAB1257F29B67B22ADAA77B1?
id=LEX-FAOC087196&index=documents. Accessed 26 Aug 2011
34. Bilingual laws information system. Department of Justice,
Government of Hong Kong. http://www.legislation.gov.hk/eng/
home.htm. Accessed 26 Aug 2011
35. An overview on air quality and air pollution control in Hong
Kong. Environmental Protection Department, Special Admin-
istrative Region, The Government of the Hong Kong. http://
www.epd.gov.hk/epd/english/environmentinhk/air/air_maincont
ent.html. Accessed 26 Aug 2011
36. Hong Kong’s environment, air. Environmental Protection
Department. http://www.epd.gov.hk/epd/english/environmentinhk/
air/air_maincontent.html. Accessed 26 Aug 2011
37. Contents of new emission regulation of volatile organic com-
pounds. Press release 2005, Ministry of Environment, Govern-
ment of Japan. http://www.env.go.jp/en/press/2005/0606a.html.
Accessed 26 Aug 2011
38. Derwent RG, Jenkin ME, Saunders SM, Pilling MJ, Simmonds
PG, Passant NR, Dollard GJ, Dumitrean P, Kent A (2003)
Photochemical ozone formation in north west Europe and its
control. Atmos Environ 37:1983–1991
39. An introduction to indoor air quality volatile organic compounds
(VOCs). U.S. Environmental Protection Agency. http://www.
epa.gov/iaq/voc.html#HealthEffects. Accessed 26 Aug 2011
40. Hester RE, Harrison RM (1995) Volatile organic compounds in
the atmosphere. Thomas Graham House, Cambridge
41. Uchiyama S, Hasegawa S (2000) Investigation of a long-term
sampling period for monitoring volatile organic compounds in
ambient air. Environ Sci Tehchnol 34:4656–4661
42. Yoon S-H, Chai X-s, Zhu JY, Li J, Malcolm EW (2001) In-
digester reduction of organic sulfur compounds in kraft pulping.
Adv Environ Res 5:91–98
43. IARC, International Agency for Research of Cancer. World
Health Organization. http://monographs.iarc.fr/ENG/Classifica
tion/ClassificationsGroupOrder.pdf. Accessed 26 Aug 2011
44. Bowman FM, Pilinis C, Seinfeld JH (1995) Ozone and aerosol
productivity of reactive organics. Atmos Environ 29(5):579–589
45. Khan FI, Ghoshal AKr (2000) Removal of volatile organic
compounds from polluted air. J Loss Prev Process Ind
13:527–545
Top Catal (2011) 54:1224–1256
46. Foster P, Ramaswamy V, Artaxo P, Berntsen T, Betts R, Fahey
DW, Haywood J, Lean J, Lowe DC, Myhre G, Nganga J, Prinn
R, Raga G, Schulz M, Van Dorland R (2007) Changes in
atmospheric constituents and in radiative forcing. In: Solomon
S, Qin D, Manning M, Chen Z, Marquis M, Averyt KB, Tignor
M, Miller HL (eds) Climate change 2007: the physical science
basis. contribution of working group I to the fourth assessment
report of the intergovernmental panel on climate change.
Cambridge University Press, Cambridge. http://www.ipcc.ch/
pdf/assessment-report/ar4/wg1/ar4-wg1-chapter2.pdf. Accessed
26 Aug 2011
47. Niinemets Ü, Loreto F, Reichstein M (2004) Physiological and
physicochemical controls on foliar volatile organic compound
emissions. Trends Plant Sci 9(4):180–186
48. Brown SK, Sim MR, Abranson MJ, Gray CN (1994) Concen-
trations of volatile organic compounds in indoor air—A review.
Indoor Air 14(2):123–134
49. Frost, Sullivan (2000) VOC marketing report
50. Garcı́a V, Pongrácz E, Muurinen E, Keiski RL (2009) Pervap-
oration of dichloromethane from multicomponent aqueous sys-
tems containing n-butanol and sodium chloride. J Membr Sci
326:92–102
51. Mikulova J, Rossignol S, Jr Barbier J, Duprez D, Kappenstein C
(2007) Characterizations of platinum catalysts supported on Ce,
Zr, Pr-oxides and formation of carbonate species in catalytic wet
air oxidation of acetic acid. Catal Today 124:185–190
52. Lintz H-G, Wittstock K (2001) The oxidation of solvents in air
on oxidic catalysts—formation of intermediates and reaction
network. Appl Catal A 216:217–225
53. Ertl G, Knözinger H, Weitkamp J (eds) (1997) Handbook of
heterogeneous catalysis, vol 1. VCH, Weinheim
54. Thomas JM, Thomas WJ (1997) Principles and practice of
heterogeneous catalysis. VCH, Weinheim
55. Willinger M, Rupp E, Barbaris B, Gao S, Arnold RG, Betterton
EA, Sáez AE (2009) Thermocatalytic destruction of gas-phase
perchloroethylene using propane as a hydrogen source. J Hazard
Mater 167:770–776
56. Gutiérrez-Ortiz JI, de Rivas B, Lop-Fonseca R, González-Velasco
JR (2004) Combustion of aliphatic C2 chlorohydrocarbons over
ceria–zirconia mixed oxides catalysts. Appl Catal A 269:147–155
57. Scire S, Minico S, Crisafulli C, Satriano C, Pistone A (2003)
Catalytic combustion of volatile organic compounds on gold/
cerium oxide catalysts. Appl Catal B 40:43–49
58. Doornkamp C, Ponec V (2000) The universal character of the
Mars–van Krevelen mechanism. J Mol Catal A 162:19–32
59. Aranzabal A, Ayastuy-Arizti JL, González-Marcos JA,
González-Velasco JR (2003) The reaction pathway and kinetic
mechanism of the catalytic oxidation of gaseous lean TCE on
Pd/alumina catalysts. J Catal 214:130–135
60. Horák J (1972) Technická heterogennı́ katalýza. Ed.; SNTL—
Nakladatelstvı́ technické literatury, Prague
61. Cullis CF, Willat BM (1983) Oxidation of methane over sup-
ported precious metal catalysts. J Catal 83:267–285
62. Burch R, Urbano FJ (1995) Investigation of the active state of
supported palladium catalysts in the combustion of methane.
Appl Catal A 124:121–138
63. Janbey A, Clark W, Noordally E, Grimes S, Tahir S (2003)
Noble metal catalysts for methane removal. Chemosphere
52:1041–1046
64. Zwinkels MFM, Haussner O, Govind Menon P, Järås SG (1999)
Preparation and characterization of LaCrO3 and Cr2O3 methane
combustion catalysts supported on LaAl11O18- and Al2O3-
coated monoliths. Catal Today 47:73–82
65. Gélin P, Primet M (2002) Complete oxidation of methane at low
temperature over noble metal based catalysts: a review. Appl
Catal B 39:1–37
1251
66. Duprez D (2006) Isotopes in catalysis, Catalytic science series 4.
Imperial College Press, London, pp 133–181
67. Yang L, Shi C, He X, Cai J (2002) Catalytic combustion of
methane over PdO supported on Mg-modified alumina. Appl
Catal B 38:117–125
68. Thevenin PO, Pocoroba E, Pettersson LJ, Karhu H, Väyrynen IJ,
Järås SG (2002) Characterization and activity of supported
palladium combustion catalysts. J Catal 207:139–149
69. Baldwin TR, Burch R (1990) Catalytic combustion of methane
over supported palladium catalysts II. Support and possible
morphological effects. Appl Catal 66:359–381
70. Marceau E, Lauron-Pernot H, Che M (2001) Influence of the
metallic precursor and of the catalytic reaction on the activity
and evolution of Pt(Cl)/d-Al2O3 catalysts in total oxidation of
methane. J Catal 197:394–405
71. Ciuparu D, Lyubovsky MR, Altman E, Pfefferle LD, Datye A
(2002) Catalytic combustion of methane over palladium-based
catalysts. Catal Rev 44(4):593–649
72. Ojala S, Lassi U, Keiski R (2006) Testing VOC emission
measurement techniques in wood-coating industrial processes
and developing a cost-effective measurement methodology.
Chemosphere 62:113–120
73. Musalik-Piotrowska A, Syczewska K (2000) Combustion of
volatile organic compounds in two-component mixtures over
monolithic perovskite catalysts. Catal Today 59:269–278
74. Taylor SH, Heneghan CS, Hutchings GJ (1998) Uranium oxide
catalysts for VOCs. Ind Catal News 3:4–9
75. Taylor SH, Heneghan CS, Hutchings GH, Hudson ID (2000)
The activity and mechanism of uranium oxide catalysts for the
oxidative destruction of volatile organic compounds. Catal
Today 59:249–259
76. Interview of Caj Karlsson, Neste Oil Naantali Refinery, 17 Aug
2010
77. Jennings MS (1985) Catalytic incineration for control of volatile
organic compound emissions. Noyes Publications, Park Ridge
78. An Energy Policy for Europe, {SEC(2007)12}, Communication
from the commission to the European Council and the European
Parliament. http://eur-lex.europa.eu/smartapi/cgi/sga_doc?smart
api!celexplus!prod!DocNumber&lg=en&type_doc=COMfinal&
an_doc=2007&nu_doc=1. Accessed 26 Aug 2011
79. Ferrandon M, Carnö J, Järås S, Björnbom E (1999) Total oxi-
dation catalysts based on manganese or copper oxides, platinum
or palladium I: characterisation. Appl Catal A 180:141–151
80. Papaefthimiaou P, Ioannides T, Verykios XE (1997) Combus-
tion of non-halogenated volatile organic compounds over group
VIII metal catalysts. Appl Catal B 13:175–184
81. Mikulová J, Rossignol S, Barbier J Jr, Mesnard D, Kappenstein
C, Duprez D (2007) Ruthenium and platinum catalysts sup-
ported on Ce, Zr, Pr-O mixed oxides prepared by soft chemistry
for acetic acid wet air oxidation. Appl Catal B 72:1–10
82. Lox ESJ, Engler BH (1997) Environmental catalysis mobile
sources. In: Ertl G, Knozinger H, Weitkamp J (eds) Handbook
of heterogeneous catalysis, vol 4. VCH, Weinheim, p 1664
83. Stone FS (1962) Chemisorption and catalysis on metallic oxides.
Adv Catal 13:1–53
84. Lamb AB, Bray WC, Frazer JCW (1920) The removal of carbon
monoxide from Air. Ind Eng Chem 12:213
85. Jones HA, Taylor HS (1923) The reduction of copper oxide by
carbon monoxide and the catalytic oxidation of carbon mon-
oxide in the presence of copper and copper oxide. J Phys Chem
27:623
86. Kovanda F, Rojka T, Dobeošvá J, Machovič V, Bezdička P,
Obalová L, Jirátová K, Grygar T (2006) Mixed oxides obtained
from Co and Mn containing layered double hydroxides: prepa-
ration, characterization, and catalytic properties. J Solid State
Chem 179:812–823
123
1252
87. Kovanda F, Grygar T, Dorničák V, Rojka T, Bezdička P, Jirá-
tová K (2005) Thermal behaviour of Cu–Mg–Mn and Ni–Mg–
Mn layered double hydroxides and characterization of formed
oxides. Appl Clay Sci 28:121
88. Čuba P, Kovanda F, Hilaire L, Jirátová K (2005) In: 4th inter-
national conference on environmental catalysis, 5–8 June 2005,
Heidelberg (poster). Abstrakt: programme/book of abstracts
89. Obalová L, Jirátová K, Kovanda F, Pacultová K, Lacný Z,
Mikulová Z (2005) Catalytic decomposition of nitrous oxide
over catalysts prepared from Co/Mg–Mn/Al hydrotalcite-like
compounds. Appl Catal B 60:289–298
90. Mikulová Z, Balabánová J, Jirátová K, Kovanda F (Eng) (2005)
In: International course: new trends in catalysis, Brussels, Pro-
ceedings, pp 199–200
91. Jirátová K, Kovanda F, Cuba P, Balabánová J, Hilaire L, Pitchon
V (2004) In: 67th Pannonian international symposium on
catalysis, Srnı́. Abstrakt: book of abstracts
92. Mikulová J, Rossignol S, Gérard F, Mesnard D, Kappenstein C,
Duprez D (2006) Properties of cerium–zirconium mixed oxides
partially substituted by neodymium: comparison with Zr–Ce–
Pr–O ternary oxides. J Solid State Chem 179:2511–2520
93. Mattos LV, Noronha FB (2005) The influence of the nature of
the metal on the performance of cerium oxide supported cata-
lysts in the partial oxidation of ethanol. J Power Sources
145:50–59
94. Jiratova K, Mikulova J, Klempa J, Grygar T, Bastl Z, Kovanda F
(2009) Modification of Co–Mn–Al mixed oxide with potassium
and its effect on deep oxidation of voc. Appl Catal A
361(1–2):106–116
95. Gaálová J, Jirátová K (2009) Effect of uranium in Co–Mn–Al
mixed oxide catalyst on deep oxidation of VOC. NANOISRAEL
2009. Jerusalem, 30 Mar 2009–31 Mar 2009, Grant: GA R
GA104/07/1400
96. Gaálová J, Jirátová K, Mikulová Z (2009) Co–Mn–Al–O cata-
lysts for oxidation of VOC: effect of promoter. In: European
conference on environmental applications of advanced oxidation
processes 2, Nicosia, 9 Sep 2009–11 Sep 2009
97. O’Malley A, Hodnett BK (1999) The influence of volatile
organic compound structure on conditions required for total
oxidation. Catal Today 54(1):31–38
98. López-Fonseca R, Gutiérrez-Ortiz JI, González-Velasco JR
(2004) Mixture effects in the catalytic decomposition of lean
ternary mixtures of chlororganics under oxidising conditions.
Catal Commun 5:391–396
99. Sinquin G, Petit C, Libs S, Hindermann JP, Kiennemann A
(2000) Catalytic destruction of chlorinated C1 volatile organic
compounds (CVOCs) reactivity, oxidation and hydrolysis
mechanism. Appl Catal B 27:105–115
100. López-Fonseca R, Cibrián S, Gutiérrez-Ortiz JI, Gutiérrez-Ortiz
M-A, González-Velasco JR (2003) Oxidative destruction of
dichloromethane over protonic zeolites. AIChE J 49(2):496–504
101. Dai Q, Wang X, Lu G (2007) Low-temperature catalytic
destruction of chlorinated VOCs over cerium oxide. Catal
Commun 8:1645–1649
102. Gutiérrez-Ortiz JI, de Rivas B, López-Fonseca R, Martı́n S,
González-Velasco JR (2007) Structure of Mn–Zr mixed oxides
catalysts and their catalytic performance in the gas-phase oxi-
dation of chlorocarbons. Chemosphere 68:1004–1012
103. Abdullah AZ, Bakar MZA, Bhatia S (2006) Combustion of
chlorinated volatile organic compounds (VOCs) using bimetallic
chromium-copper supported on modified H-ZSM-5 catalyst.
J Hazard Mater B 129:39–49
104. Van den Brink RW, Mulder P, Louw R, Sinquin G, Petit C,
Hindermann J-P (1998) Catalytic oxidation of dichloromethane
on c-Al2O3: a combined flow and infrared spectroscopic study.
J Catal 180:153–160
123
Top Catal (2011) 54:1224–1256
105. Alberici RM, Mendes MA, Jardim WF, Eberlin MN (1998)
Mass spectrometry on-line monitoring and MS2 product char-
acterization of TiO2/UV photocatalytic degradation of chlori-
nated volatile organic compounds. Am Soc Mass Spectrom 9:
1321–1327
106. Everaert K, Baeyens J (2004) Catalytic combustion of volatile
organic compounds. J Hazard Mater B109:113–139
107. González-Velasco JR, Aranzabal A, López-Fonseca R, Ferret R,
González-Marcos JA (2000) Enhancement of catalytic oxidation
of hydrogen-lean chlorinated VOCs in the presence of hydro-
gen-supplying compounds. Appl Catal B 24:33–43
108. Corella J, Toledo JM, Padilla AM (2000) On the selection of the
catalyst among the commercial platinum-based ones for total
oxidation of some chlorinated hydrocarbons. Appl Catal B
27:243–256
109. Gonzáles-Velasco JR, Aranzabal A, Gutiérrez-Ortiz JI, López-
Fonseca R, Gutiérrez-Ortiz MA (1998) Activity and product
distribution of alumina supported platinum and palladium cat-
alysts in the gas-phase oxidative decomposition of chlorinated
hydrocarbons. Appl Catal B 19:189–197
110. Musialik-Piotrowska A, Syczewska K (2002) Catalytic oxida-
tion of trichloroethylene in two-component mixtures with
selected volatile organic compounds. Catal Today 73:333–342
111. Koyer-Golkowska A, Musialik-Piotrowska A, Rutkowski JD
(2004) Oxidation of chlorinated hydrocarbons over Pt–Pd-based
catalyst Part 1. Chlorinated methanes. Catal Today 90:133–138
112. Chen B, Bai C, Cook R, Wright J, Wang C (1996) Gold/cobalt
oxide for oxidative destruction of dichloromethane. Catal Today
30:15–20
113. Padilla AM, Corella J, Toledo JM (1999) Total oxidation of
some chlorinated hydrocarbons with commercial chromia based
catalysts. Appl Catal B 22:107–121
114. Windawi H, Zhang ZC (1996) Catalytic destruction of haloge-
nated air toxics and the effect of admixture with VOCs. Catal
Today 30:99–105
115. Yim SD, Chang K-H, Koh DJ, Nam I-S, Kim YG (2000) Cat-
alytic removal of perchloroethylene (PCE) over supported
chromium oxide catalysts. Catal Today 63:215–222
116. Yim SD, Koh DJ, Nam I-S (2002) A pilot plant study for cat-
alytic decomposition of PCDDs/PCDFs over supported chro-
mium oxide catalysts. Catal Today 75:269–276
117. Chintawar PS, Greene HL (1997) Decomposition characteristics
of chlorinated ethylenes on metal loaded zeolite Y and c-Al2O3.
Appl Catal B 13:81–92
118. Wang L, Sakurai M, Kameyama H (2008) Catalytic oxidation of
dichloromethane and toluene over platinum alumite catalyst.
J Hazard Mater 154:390–395
119. Pitkäaho S, Ojala S, Maunula T, Savimäki A, Kinnunen T,
Keiski RL (2011) Oxidation of dichloromethane and perchlo-
roethylene alone and in mixtures. Appl Catal B-Environ
102:395–403
120. Orbay Ö, Gao S, Barbaris B, Rupp E, Sáez AE, Arnold RG,
Betterton EA (2008) Catalytic dechlorination of gas-phase per-
chloroethylene under mixed redox conditions. Appl Catal B
79:43–52
121. Musialik-Piotrowska A (2007) Destruction of trichloroethylene
(TCE) and trichloromethane (TCM) in the presence of selected
VOCs over Pt-Pd-based catalyst. Catal Today 119:301–304
122. de Rivas B, Lopez-Fonseca R, Sampedro C, Gutierrez-Ortiz JI
(2009) Catalytic behaviour of thermally aged Ce/Zr mixed
oxides for the purification of chlorinated VOC-containing gas
streams. Appl Catal B 90:545–555
123. de Rivas B, Lopez-Fonseca R, Gutierrez-Ortiz MA, Gutierrez-
Ortiz JI (2009) Role of water and other H-rich additives in the
catalytic combustion of 1, 2-dichloroethane and trichloroethyl-
ene. Chemosphere 75:1356–1362
Top Catal (2011) 54:1224–1256
124. Pengpanich S, Meeyoo V, Rirksomboon T, Bunyakiat K (2002)
Catalytic oxidation of methane over CeO2–ZrO2 mixed oxide
solid solution catalysts prepared via urea hydrolysis. Appl Catal
A 234:221–233
125. Trovarelli A, Leitenburg CD, Boaro M, Dolcetti G (1999) The
utilization of ceria in industrial catalysis. Catal Today
50:353–367
126. Gluhoi AC, Bogdanchikova N, Nieuwenhuys BE (2005) The
effect of different types of additives on the catalytic activity of
Au/Al2O3 in propene total oxidation: transition metal oxides and
ceria. J Catal 229:154–162
127. Kaspar J, Fornasiero P (2002) Structural properties and thermal
stability of ceria–zirconia and related materials. In: Trovarelli A
(ed) Catalysis by ceria and related materials, Catalytic science
series, vol 2. Imperial College Press, London, pp 217–241
128. Kantzer E, Döbber D, Kießling D, Wendt G (2002) MnOx/
CeO2–ZrO2 and MnOx/WO3–TiO2 catalysts for the total oxi-
dation of methane and chlorinated hydrocarbons. Stud Surf Sci
Catal 143:489–497
129. Lahousse C, Bernier A, Grange P, Delmon B, Papaefthimiou P,
Ioannides T, Verykios X (1998) Evaluation of g-MnO2 as a
VOC removal catalyst: comparison with a noble metal catalyst.
J Catal 178:214–225
130. Xu Z, Inumaru K, Yamanaka S (2001) Catalytic properties of
metal loaded silica-pillared manganese titanate for CO oxida-
tion. Appl Catal A 210:217–224
131. Kang M, Park ED, Kim JM, Yie JE (2006) Cu–Mn mixed oxides
for low temperature NO reduction with NH3. Catal Today
111:236–241
132. Vu VH, Belkouch J, Ould-Dris A, Taouk B (2009) Removal of
hazardous chlorinated VOCs over Mn–Cu mixed oxide based
catalyst. J Hazard Mater 169:758–765
133. Ojala S, Lassi U, Ylönen R, Keiski R, Laakso I, Maunula T,
Silvonen R (2005) Abatement of malodorous pulp mill emis-
sions by catalytic oxidation—pilot experiments in Stora Enso
Pulp Mill, Oulu, Finland. Tappi J 4:1–6
134. Flagan RC, Seinfeld JH (1988) Fundamentals of air pollution
engineering. Prentice-Hall, Englewood Cliffs
135. De Nevers N (2000) Air pollution control engineering. McGraw-
Hill, New York
136. Jones JM, Dupont VA, Brydson R, Fullerton DJ, Nasri NS, Ross
AB, Westwood AVK (2003) Sulphur poisoning and regenera-
tion of precious metal catalysed methane combustion. Catal
Today 81:589–601
137. Mahzoul H, Limousy L, Brilhac JF, Gilot P (2000) Experimental
study of SO2 adsorption on barium-based NOx adsorbers. J Anal
Appl Pyrol 56:179–193
138. Ross RA, Sood SP (1977) Catalytic oxidation of methyl
mercaptan over cobalt molybdate. Ind Eng Chem 16(2):147–
150
139. Dalai AK, Tollefson EL, Yang A, Sasaoka E (1997) Oxidation
of methyl mercaptan over an activated carbon in a fixed-bed
reactor. Ind Eng Chem Res 36:4726–4733
140. Chu H, Horng K (1998) The kinetics of the catalytic incineration
of CH3SH and (CH3)2S over a Pt/Al2O3 catalyst. Sci Total
Environ 209:149–156
141. Kastner JR, Das KC, Melear ND (2002) Catalytic oxidation of
gaseous reduced sulfur compounds using coal fly ash. J Hazard
Mater B95:81–90
142. Kastner JR, Das KC, Buquoi Q, Melear ND (2003) Low tem-
perature catalytic oxidation of hydrogen sulfide and metha-
nethiol using wood and coal fly ash. Environ Sci Technol
37(11):2568–2574
143. Wang C-H, Weng H-S (1997) Al2O3-supported mixed-metal
oxides for destructive oxidation of (CH3)2S2. Ind Eng Chem Res
36:2537–2542
1253
144. Martı́nez E, Albaladejo J, Notario A, Jiménez E (2002) A study
of the atmospheric reaction of CH3S with O3 as a function of
temperature. Atmos Environ 34:5295–5302
145. Butt JB, Petersen EE (1988) Activation, deactivation and poi-
soning of catalysts. Academic Press, New York
146. Chu H, Hao GH, Tseng TK (2003) Laboratory study of poi-
soning of a MnO/Fe2O3 catalyst by dimethyl sulfide and dime-
thyl disulfide. J Hazard Mater 100(1–3):209–218
147. Bashkova S, Bagreev A, Bandosz TJ (2005) Catalytic properties
of activated carbon surface in the process of adsorption/oxida-
tion of methyl mercaptan. Catal Today 99:323–328
148. Chang J-R, Chang S-L, Lin T-B (1997) c-Alumina-supported Pt
catalysts for aromatics reduction: a structural investigation of
sulfur poisoning catalyst deactivation. J Catal 169:338–346
149. Meyoo V, Trimm DL, Cant NW (1998) The effect of sulphur
containing pollutants on the oxidation activity of precious
metals used in vehicle exhaust catalysts. Appl Catal B 16:L101–
L104
150. Lee J-K, Rhee H-K (1998) Sulfur tolerance of zeolite beta-
supported Pd–Pt catalysts for the isomerization of n-hexane.
J Catal 177:208–216
151. Ferrandon M, Carnö J, Järås S, Björnbom E (1999) Total oxi-
dation catalysts based on manganese or copper oxides and
platinum or palladium II: activity, hydrothermal stability and
sulphur resistance. Appl Catal A 180:153–161
152. Corro G, Montiel R, Carlos Vázquez L (2002) Promoting and
inhibiting effect of SO2 on propane oxidation over Pt/Al2O3.
Catal Commun 3:533–539
153. Skoglundh M, Ljungqvist A, Petersson M, Fridell E, Cruise N,
Augustsson O, Jobson E (2001) SO2 promoted oxidation of ethyl
acetate, ethanol and propane. Appl Catal B 30:315–328
154. Corti CW, Holliday RJ, Thompson DT (2005) Commercial
aspects of gold catalysis. Appl Catal B 291:253–261
155. Rodrigues JA (2006) The chemical properties of bimetallic
surfaces: Importance of ensemble and electronic effects in the
adsorption of sulphur and SO2. Prog Surf Sci 81:141–189
156. Ojala S, Mikkola JP, Keiski R (2008) Application of Au cata-
lysts in TRS emission abatement. In: 18th international congress
of chemical and process engineering, CHISA 2008, Book of
abstracts, Prague
157. Campanati M, Fornasari G, Vaccari A (2003) Fundamentals in
the preparation of heterogeneous catalysts. Catal Today
77(4):299–314
158. Brahmi R, Batonneau Y, Kappenstein C, Miotti P, Tajmar M,
Scharlemann C, Lang M (2006) Ceramic catalysts for the
decomposition of H2O2. Stud Surf Sci Catal 162:649–656
159. Lifeng W, Makoto S, Hideo K (2009) Study of catalytic
decomposition of formaldehyde on Pt/TiO2 alumite catalyst at
ambient temperature. J Hazard Mater 167:399–405
160. Zhidong J, Ki-Suk C, Gun-Rae K, Jong-Shik C (2003) Mass
transfer characteristics of wire-mesh honeycomb reactors. Chem
Eng Sci 58:1103–1111
161. Valentini M, Groppi G, Cristiani C, Levi M, Tronconi E,
Forzatti P (2001) The deposition of [gamma]-Al2O3 layers on
ceramic and metallic supports for the preparation of structured
catalysts. Catal Today 69(1–4):307–314
162. Kikuchi H, Onuma T, Kamijo M (2001) Jp Patent 2001232212
163. Abe A, Yoshida K (1992) Jp Patent 04027441
164. Tao T, Xie Y, Dawes S, Melscoet-Chauvel I, Pfeifer M, Spurk
PC (2004) Diesel SCR NOx reduction and performance on
washcoated SCR catalysts. Society of Automotive Engineers,
SP-1860, Diesel exhaust emiss control, pp 367–375
165. Lojewska J, Kolodziej A, Dynarowicz-Latka P, Weselucha-
Birczynska A (2005) Engineering and chemical aspects of the
preparation of microstructured cobalt catalyst for VOC com-
bustion. Catal Today 101:81–91
123
1254
166. Yang KS, Choi JS, Chung JS (2004) Evaluation of wire-mesh
honeycomb containing porous Al/Al2O3 layer for catalytic
combustion of ethyl acetate in air. Catal Today 97(2–3):159–165
167. An S, Lee J, Brahmi R, Kappenstein C, Kwon S (2010) Com-
parison of catalyst support between monolith and pellet in
hydrogen peroxide thrusters. J Propuls Power 26(3):439–445
168. Cybulski A, Moulijn JA (1994) Monoliths in heterogeneous
catalysis. Catal Rev Sci Eng 36:179–270
169. Mazzarino I, Barresi AA (1993) Catalytic combustion of VOC
mixtures in a monolithic reactor. Catal Today 17:335–348
170. Geus JW, van Giezen JC (1999) Monoliths in catalytic oxida-
tion. Catal Today 47(1–4):169–180
171. Boix AV, Zamaro JM, Lombardo EA, Miro EE (2003) The
beneficial effect of silica on the activity and thermal stability of
PtCoFerrierite-washcoated cordierite monoliths for the SCR of
NOx with CH4. Appl Catal B 46(1):121–132
172. Murata Y, Satokawa S, Yamaseki K-I, Yamamoto H, Uchida H,
Yahagi M, Yokota H (1999) Development of the new NOx
reduction catalyst with hydrocarbons and the cleanup systems of
exhaust gases for lean-burn gas engines. In: Proceedings of the
ASME advanced energy systems division, vol 39. American
Society of Mechanical Engineers (AES), New York, pp 447–451
173. Bodke AS, Bharadwaj SS, Schmidt LD (1998) The effect of
ceramic supports on partial oxidation of hydrocarbons over
noble metal coated monoliths. J Catal 179(1):138–149
174. Thevenin PO, Ersson AG, Kusar HMJ, Menon PG, Jaras SG
(2001) Deactivation of high temperature combustion catalysts.
Appl Catal A 212(1–2):189–197
175. Boger TR, Roy S, Sorensen CM (2004) Us Patent 2004004031
176. Liu D, Zhang Y, Fan Y, Gui G, Wei X (2002) Cn Patent
1365854
177. Xu X, Vonk H, Cybulski A, Moulijn JA (1995) Alumina
washcoating and metal deposition of ceramic monoliths. Stud
Surf Sci Catal 91:1069–1078
178. Shen M, Wang J, Weng D, Han S, He F (2004) Study on thermal
durability and modification mechanism of washcoat for cordi-
erite monolith substrate. Zhongguo Xitu Xuebao 22(4):527–531
179. Yang Z, Chen X, Niu G, Liu Y, Bian M, He A-D (2001)
Comparison of effect of La-modification on the thermostabilities
of alumina and alumina-supported Pd catalysts prepared from
different alumina sources. Appl Catal B 29(3):185–194
180. Ding H, Weng D, Wu X (2000) Effect of rare earth on the
thermostability and the surface area of auto-catalyst washcoats.
J Alloys Compd 311(1):26–29
181. Hamad A, Fayed ME (2004) Simulation-aided optimization of
volatile organic compounds recovery using condensation. Chem
Eng Res Des 82(A7):895–906
182. Ojala S (2003) Measurement and abatement of volatile organic
compounds: focus on catalytic oxidation. Licentiate thesis.
University of Oulu, Oulu
183. Khan FI, Ghosal AKr (2000) Removal of volatile organic
compounds from polluted air. J Loss Prev Proc Ind 13:527–545
184. Heck RM, Farrauto RJ (1995) Catalytic air pollution control—
commercial technology. Van Nostrand Reinhold, New York
185. Breen JP, Burch R, Kulkarni M, McLaughlin D, Collier PJ,
Golunski SE (2007) Improved selectivity in the toluene alkyl-
ation reaction through understanding and optimising the process
variables. Appl Catal A 316:53–60
186. Ojala S, Lassi U, Perämäki P, Keiski RL (2008) Effects of
process parameters on catalytic incineration of solvent emis-
sions. J Autom Methhods Manag Chem 2008:1–7
187. Heneghan CS, Hutchings GJ, Taylor SH (2004) The destruction
of volatile organic compounds by heterogeneous catalytic oxi-
dation. In: Spivey JJ (ed) Catalysis, vol 7. Royal Society of
Chemistry, Cambridge, pp 105–149
123
Top Catal (2011) 54:1224–1256
188. Pitkäaho S, Ojala S, Kinnunen T, Silvonen R, Keiski RL (2011)
Catalytic oxidation of dichloromethane and perchloroethylene—
laboratory vs. industrial scale study. Top Catal. doi:10.1007/
s11244-011-9748-0
189. Burch R, Crittle DJ, Hayes MJ (1999) C–H bond activation in
hydrocarbon oxidation on heterogeneous catalysts. Catal Today
47:229–234
190. LylykangasR (1996) Kemira Oy, Poistokaasujen polttolaitteisto.
FI Patent 97080
191. Ojala S, Lassi U, Härkönen M, Maunula T, Silvonen R, Keiski
RL (2005) Durability of VOC catalysts in solvent emission
oxidation. Chem Eng J 120(2006):11–16
192. Trimm DL (2001) The regeneration or disposal of deactivated
heterogeneous catalysts. Appl Catal A 212:153–160
193. Riihimäki M (2002) Development of recuperative heat
exchanger to a catalytic oxidizer. Master Thesis, University of
Oulu, Oulu
194. Kolios G, Frauhammer J, Eigenberger G (2002) Efficient reactor
concepts for coupling of endothermic and exothermic reactions.
Chem Eng Sci 57:1505–1510
195. Matros YuSh (1990) Performance of catalytic processes under
unsteady conditions. Chem Eng Sci 45(8):2097–2102
196. Sheintuch M (2005) Analysis of design sensitivity of flow-
reversal reactors: simulations, approximations and oxidation
experiments. Chem Eng Sci 60:2991–2998
197. Nicken U, Kolios G, Eigenberger G (1994) Eigenberger fixed-
bed reactors with periodic flow reversal: experimental results for
catalytic combustion. Catal Today 20:335–350
198. de Wit J, Johansen K, Hansen PL, Rossen H, Rasmussen NB
(2000) Catalytic emission control with Respect to CH4 and CO
for highly efficient gas fueled decentralised heat and power
production. In: 5th international conference on furnaces and
boilers (infub), Porto
199. Rafidi M, Blasiak W (2005) Thermal performance analysis on a
two composite material honeycomb heat regenerators used for
HiTAC burners. Appl Therm Eng 25:2966–2982
200. Fujishima A, Zhang X, Tryk DA (2008) TiO2 photocatalysis and
related surface phenomena. Surf Sci Rep 63:515–582
201. Paz Y (2010) Application of TiO2 photocatalysis for air treat-
ment: patents’ overview. Appl Catal B 99:448–460
202. SP3 (2010) Third international conference on semiconductor
photochemistry, Book of abstracts, University of Strathclyde,
Glasgow
203. Zuo G-M, Cheng Z-X, Chen H, Li G-W, Miao T (2006) Study
on photocatalytic degradation of several volatile organic com-
pounds. J Hazard Mater B 128:158–163
204. Akly C, Chadik PA, Mazyck DW (2010) Photocatalysis of gas-
phase toluene using silica-titania composites: performance of a
novel catalyst immobilization technique suitable for large-scale
applications. Appl Catal B 99:329–335
205. Benoit-Marquié F, Wilkenhöner U, Simon V, Braun AM,
Oliveros E, Maurette M-T (2000) VOC photodegradation at the
gas-solid interface of a TiO2 photocatalyst. Part I: 1-butanol and
1-butylamine. J Photochem Photobiol A 132:225–232
206. Mo J, Zhang Y, Xu Q, Lamson JJ, Zhao R (2009) Photocatalytic
purification of volatile organic compounds in indoor air: a lit-
erature review. Atmos Environ 43:2229–2246
207. Van Durme J, Dewulf J, Leys C, Van Langenhove H (2008)
Combining non-thermal plasma with heterogeneous catalysis in
waste gas treatment. Appl Catal B 78:324–333
208. Roland U, Holzer F, Kopinke F-D (2002) Improved oxidation of
air pollutants in a non-thermal plasma. Catal Today 72:315–323
209. Magureanu M, Mandache NB, Eloy P, Gaigneaux EM,
Parvulescu VI (2005) Plasma-assisted catalysis for volatile
organic compounds abatement. Appl Catal B 61:12–20
Top Catal (2011) 54:1224–1256
210. Futamura S, Zhang A, Einaga H, Kabashima H (2002)
Involvement of catalyst materials in nonthermal plasma chem-
ical processing of hazardous air pollutants. Catal Today 72:
259–265
211. Harling AM, Demidyuk V, Fischer SJ, Whitehead JC (2008)
Plasma-catalysis destruction of aromatics for environmental
clean-up: effect of temperature and configuration. Appl Catal B
82:180–189
212. Besov AS, Vorontsov AV (2007) Acceleration of acetone
destruction process under synergistic action of photocatalytic
oxidation and barrier discharge. Plasma Chem Plasma Process
27(5):624–634
213. Vorontsov A, Besov A, Trubitsyn D, Lulukin M, Parmon V
(2010) Acceleration of air purification by combining photoca-
talysis and electric discharge. In: Book of abstracts, SP3 third
international conference on semiconductor photochemistry,
Glasgow
214. Kucherov AV, Sinev IM, Slovetskaya KI, Ojala S, Keiski R,
Golosman EZ, Kustov LM (2008) CuO–MnO2 oxidation cata-
lyst: energy-saving VOC and S-VOC removal from air in iso-
thermal and periodical microwave-assisted processes. In: 13th
nordic symposium on catalysis, Goteborg, Book of abstracts
215. Kucherov AV, Sinev IM, Ojala S, Keiski R, Kustov LM (2007)
Adsorptive-catalytic removal of CH3OH, CH3SH, and
CH3SSCH3 from air over the bifunctional system noble metals/
HZSM-5. Stud Surf Sci Catal 170:1129–1136
216. Menéndez JA, Arenillas A, Fidalgo B, Fernández Y, Zubizarreta
L, Calvo EG, Bermúdez JM (2010) Microwave heating pro-
cesses involving carbon materials. Fuel Process Technol 91:1–8
217. Ighigeanu D, Calinescu I, Martin D, Matei C (2008) A new
hybrid technique for the volatile organic compounds removal by
combined use of electron beams, microwaves and catalysts.
Nucl Instrum Methhods Phys Res Sec B 266:2523–2528
218. Takashima H, Karches M, Kanno Y (2008) Catalytic decom-
position of trichloroethylene over Pt-/Ni-catalyst under micro-
wave heating. Appl Surf Sci 254:2023–2030
219. Zhang X, Hayward DO (2006) Applications of microwave
dielectric heating in environment-related heterogeneous gas-
phase catalytic systems. Inorg Chim Acta 359:3421–3433
220. Horikoshi S, Serpone N (2009) Photochemistry with micro-
waves, catalysts and environmental applications. J Photochem
Photobiol C 10:96–110
221. Polaert I, Estel L, Huyghe R, Thomas M (2010) Adsorbents
regeneration under microwave irradiation for dehydration and
volatile organic compounds gas treatment. Chem Eng J
170:338–341
222. Lassi U (2003) Deactivation correlations of Pd/Rh three-way
catalysts designed for Euro IV emission limits. Doctoral thesis,
University of Oulu, Oulu
223. Sillanpää M, Saari J, Dahl O (1993) Sellun pesun perusmek-
anismit. Department of Process Engineering, University of Oulu,
Oulu, report 236
224. Teir S, Elovena S, Zevenhoven R (2005) Production of precip-
itated calcium carbonate from calcium silicates and carbon
dioxide. Energy Conv Manag 46:2954–2979
225. Ehtonen P, Sarwar G, Hurme M (2004) Chemical pulp pro-
duction: focus on the environmental friendly and economical
modern processes. Paperi ja Puu–Pap Timber 86(4):269–277
226. Koukkari P, Pakarinen H, Leino H (2002) Hiilidioksidi
hyötykäyttöön paperitehtaassa. Kemia-Kemi 29(3):24–27
227. Burgess TL, Gibson AG, Furstein SJ, Wachs IE (2002) Con-
verting waste gases from pulp mills into value-added chemicals.
Environ Prog 21:137–141
228. Chai XS, Dhasmana B, Zhu JY (1998) Formation of volatile
organic compounds (VOC’s) during pulping, IPST Technical
1255
Paper Series Number 709, Institute of Paper Science and
Technology, Atlanta
229. Garner J (1996) Methanol emission control meet EPA ‘‘cluster’’
requirements. Pulp Pap 70(8):59–62
230. Wachs IE (1999a) Treating methanol-containing waste gas
streams. US Patent 5907066
231. Gutierrez L, Mueller J, Walden C (1978) Steam stripping of
condensates removes TRS contaminants. Pulp Pap Can
79(9):T280–T284
232. Bordado JCM, Gomes JFP (2002) Atmospheric emissions of
Kraft pulp mills. Chem Eng Process 41:667–671
233. Jacoby M (2002) Catalytic cleanup at the pulp mill. Chem Eng
News 80(12):39–40
234. Gerberich HR, Seaman GC (1994) Formaldehyde. In: Kroschwitz
J (ed) Kirk-Othmer encyclopedia of chemical technology, vol 11.
Wiley, New York, pp 929–950
235. Ai M (1978) Catalytic activity for the oxidation of methanol and
the acid–base properties of metal oxides. J Catal 54:426–435
236. Mann RS, Dosi MK (1973) Kinetics of vapour-phase oxidation
of methyl alcohol on vanadium pentoxide-molybdenum trioxide
catalyst. J Catal 28:282–288
237. Cheng W-H (1996) Methanol and formaldehyde oxidation study
over molybdenum oxide. J Catal 158:477–485
238. Soares APV, Portela MF, Kiennemann A, Hilaire L, Millet JMM
(2001) Iron molybdate catalysts for methanol to formaldehyde
oxidation: effects of Mo excess on catalytic behaviour. Appl
Catal A 206:221–229
239. Kijenski J, Baiker A, Glinski M, Dollenmeier P, Wokaun A
(1986) Monolayers and double layers of vanadium pentoxide on
different carriers: preparation, characterization and catalytic
activities. J Catal 101:1–11
240. Isaguliants GV, Belomestnykh IP (2005) Selective oxidation of
methanol to formaldehyde over V–Mg–O catalysts. Catal Today
100:441–445
241. Deo G, Wachs IE (1994) Reactivity of Supported vanadium
oxide catalysts: the partial oxidation of methanol. J Catal
146:323–334
242. Roozeboom F, Cordingley PD, Gellings PJ (1981) Oxide
monolayer catalysts, the vapor-phase oxidation of methanol.
J Catal 68:464–472
243. Zhao H, Bennici S, Cai J, Shen J, Auroux A (2010) Effect of
vanadia loading on the acidic, redox and catalytic properties of
V2O5–TiO2 and V2O5–TiO2/SO42- catalysts for partial oxida-
tion of methanol. Catal Today 152:70–77
244. Gambaro LA (2004) Methanol adsorption–oxidation over
V2O5—a mass spectrometry study. J Mol Catal A 214:287–291
245. Feng T, Vohs JM (2004) A TPD study of the partial oxidation of
methanol to formaldehyde on CeO2-supported vanadium oxide.
J Catal 221:619–629
246. Kim T, Wachs IE (2008) CH3OH oxidation over well-defined
supported V2O5/Al2O3 catalysts: influence of vanadium oxide
loading and surface vanadium–oxygen functionalities. J Catal
255:197–205
247. Wang Q, Madix RJ (2002) Partial oxidation of methanol to
formaldehyde on a model supported monolayer vanadia catalyst:
vanadia on TiO2(110). Surf Sci 496:51–63
248. Wachs IE (1999) Production of formaldehyde from methyl
mercaptans. US Patent 59069191
249. Sahle-Demessie E, Devulapelli VG (2008) Vapor phase oxida-
tion of dimethyl sulphide with ozone over V2O5/TiO2 catalyst.
Appl Catal B 84:408–419
250. Sahle-Demessie E, Devulapelli VG (2009) Oxidation of meth-
anol and total reduced sulphur compounds with ozone over
V2O5/TiO2 catalyst: effect of Humidity. Appl Catal A
361:72–80
123
1256 Top Catal (2011) 54:1224–1256

251. Koivikko N, Laitinen T, Pitkaaho S, Ojala S, Keiski RL (2011) 252. Koltsakis GC, Stamatelos AM (1997) Catalytic automo-
Formaldehyde production from methanol and methyl mercaptan tive exhaust aftertreatment. Prog Energy Combust Sci 23:
over titania and vanadia based catalysts. Appl Catal B 1–39
103:72–78

123