Applied Catalysis A: General 311 (2006) 112–121

www.elsevier.com/locate/apcata

State-of-the-art in the monolithic catalysts/reactors

Vesna Tomašić *, Franjo Jović
Department of Reaction Engineering and Catalysis, Faculty of Chemical Engineering and Technology,
University of Zagreb, Marulićev trg 19, 10000 Zagreb, Croatia
Received 22 August 2005; received in revised form 2 June 2006; accepted 9 June 2006
Available online 21 July 2006

Abstract
According to some authors development of monolithic catalysts and/or reactors has been one of major achievements in the field of
heterogeneous catalysis and chemical reaction engineering of the recent years. This work is aimed at pointing out the advantages of monolithic
catalysts and/or reactors with respect to the conventional ones, with particular focus on the integral approach to the catalyst and reactor design.
The paper is divided into several parts. The first part gives basic definitions and classification of monolithic catalysts, including basic features of
the monoliths and factors that have proceeded to the development and application of the monolith structures. It is explained that monoliths belong
to the class of the catalytic reaction systems, where usual differences between catalysts and reactors, arising from their action level, are
diminishing. Second part of paper is devoted to the preparation of monolithic catalysts. Next part deals with their commercial application with
particular emphasis on the less known applications, and those which are still under development. The paper concludes with forecast of potential
monoliths applications and ends up with the future research priorities and directions.
# 2006 Elsevier B.V. All rights reserved.

Keywords: Monolithic catalysts and/or reactors; Properties; Preparation; Application

1. Introduction significant energy recovery and space saving. Besides others,

such links are possible with the use of multifunctional reactors
In the last decade of the 20th century chemical and related (such as monolith and membrane reactors, catalytic filters),
process industries have come up with new trend focused on reactive distillation columns, etc. Monolithic catalysts and/or
sustainable development [1–3]. Generally, clean and/or reactors are representatives of the system in which common
sustainable technologies underpin diverse products and differences between a catalyst and a reactor disappear relevant
services that deliver performance at lower costs, greatly reduce to the micro-scale and meso-scale level [1,4–7]. This work is
or eliminate environmental impact and, in doing so, improve aimed at describing basic features of the monolithic structures,
the quality of life. The catalysts are the key for sustainable and their importance in development of environmentally
development in the chemical process industry. They help us to acceptable technologies.
synthesize product in a resource protective way, with less
consumption of energy and, in some cases, without any 1.1. Monoliths
formation of byproducts and waste. The catalysts, especially if
they are applied in a structured way, play important role in the 1.1.1. Basic definitions and classification
so-called integrated approach to environmental protection, The term ‘‘monolith’’ has its origin in Greek language. It is a
which, among others, includes integration of various process combining form of mono means ‘‘single’’ and lithos means
operations such as chemical reaction, separation, heat exchange ‘‘stone’’ [8]. A monolith structure is sometimes referred to as a
and momentum transfer. The result of the process integration is ‘‘honeycomb structure’’ [9], although in technical context
the reduction of investment costs, which is often combined with ‘‘monolith’’ has a much broader meaning, generally referred to
as the large uniform block of a single building material. In
heterogeneous catalysis it is applied mostly as a support of a
* Corresponding author. Tel.: +385 1 4597 133; fax: +385 1 4597 133. catalytically active component or as a catalyst (if a catalytic
E-mail addresses: [email protected] (V. Tomašić), [email protected] (F. Jović). component is integral part of the monolith structure).
0926-860X/$ – see front matter # 2006 Elsevier B.V. All rights reserved.
doi:10.1016/j.apcata.2006.06.013
 V. Tomašić, F. Jović / Applied Catalysis A: General 311 (2006) 112–121 113

With respect to their basic construction material there are catalytically active component. The catalysts, such as zeolites,
ceramic and metallic monoliths [4–14]. Consequently, the that do not need a specific support material, can be coated or
monoliths are made either of ceramic (mainly cordierite) or of synthesized directly on the monolithic support. Metallic
metallic materials (stainless steel, metal alloys, etc.). Schematic monoliths are prepared by thermal, chemical and electro-
presentation of a ceramic monolithic catalyst is shown in Fig. 1 chemical procedures for coating of metallic monolith structure
[15]. with the support material and a catalytically active component.
A monolithic catalyst is most commonly made by applying Relevant to wall porosity two different types of ceramic
the layer of a catalytically active component or appropriate monoliths can be distinguished: porous monoliths and
support (e.g. g-Al2O3, SiO2, ZrO2, carbon, zeolites, etc.) monoliths of a limited porosity. Most metallic monoliths are
containing one or more catalytically active components (Pt, Pd, nonporous. There is a third group of monolithic catalysts
Rh, zeolites, etc.) to the walls (or inside the walls) of the basic, distinguished by their basic structure (e.g. integral or
most frequently inert monolith structure. This process is known incorporated monoliths). The examples are monolithic catalysts
as coating or washcoating. If the monolith structure is available comprising only catalytically active components or appropriate
in the required support material, the catalytically active phase mixtures of catalytically active components (V2O5/TiO2,
can be directly deposited on the monolith. However, if the zeolites, combinations such as TiO2, V2O5 and WO3, VOx/
monolith is not available in the required support material then TiO2/SiO2, etc.) [10,12,24,25]. Such monoliths are often used
this support material should be coated on the monolithic in the treatment of exhaust gases generated in the stationary
substrate first. Generally, the leading manufacturers of the sources (e.g. during selective reduction of nitrogen oxides
monolith catalysts keep the chemical composition of the (NOx) with ammonium as a reductant) [24,25]. Their main
catalyst support material strictly confidential. In automotive advantage over previously described structures, provided
emission control it is the mixture of Al2O3, CeO2 and ZrO2 as porosity is satisfactory, is a higher specific surface.
main components with insignificant amounts of other
components (CaO, MgO, oxides of rare earth elements, etc.). 1.1.2. Basic properties of the monoliths
It is crucial that the support of a catalytically active Generally speaking, monolith structure of a catalyst has
component(s) adheres well to the basic inert monolith structure. numerous advantages over conventional particle catalysts.
This can be accomplished using appropriate additives (ceramic These include: high specific surface, small pressure drop, good
monoliths) or by the appropriate thermal and/or chemical interphase mass transfer, mostly insignificant resistance to mass
pretreatment of the metal surface (metallic monoliths). A transfer by intraphase diffusion through a catalytic layer (which
support layer can be applied to the ceramic monolith structure is usually very thin), good thermal and mechanical properties,
by various methods: (a) with colloidal solution of the simple scale up and other advantages which make them
appropriate support (the support is in the form of suspended superior related to conventional catalysts [1,9,1–14,26,27].
particles), (b) with sol–gel method (the support is in the liquid To be so efficient, monolith catalysts must comply with
phase) and (c) with adequate suspensions and other procedures many requirements [9–12,14,26,27] which include: low heat
[11,12,16]. At further steps, so prepared support is coated with a capacity, high mechanical strength and chemical stability, high
catalytically active component by conventional methods for resistance to high temperatures, temperature shocks and
catalyst preparation (impregnation, ion exchange, (co)precipi- vibrations as well as high efficiency in the presence of fast
tation, etc.) [17–20], methods as ‘‘in situ’’ zeolite crystal- changes in feed composition. They must have good heat
lization on the walls of the inert monolith structure [21–23] and conductivity to allow rapid heating of the catalyst to the
other methods. In some instances a catalytically active operating temperature which ensures satisfactory catalytic
component and a support material can be coated on the basic activity. Furthermore, it is important to find a washcoat that has
monolith structure simultaneously so as to achieve required a thermal expansion of the same order of magnitude as the
porosity, good mechanical properties and high dispersion of a support to prevent rupture (or cracks) between the washcoat
layer and support. These requirements can be met by
optimizing geometric and physical properties of both monolith
substrate and catalytic washcoat.
Basic monolith structure, depending on the purpose, varies
in dimensions and shapes (most frequently it is oval (or elliptic)
and square) [1,12]. Monolith channels or cells may be
hexagonal, rectangular or various other shapes. The ceramic
monoliths used as catalyst supports in automobile exhaust
purifier systems generally consist of a closely packed array of
small square cells. The channel walls may be of different
thickness. The geometric and physical properties of the
monoliths, such as its shape, size of the channels, thickness
and porosity of the wall as well as thickness and microstructure
of the catalytic layer depend on specific requirements of the
Fig. 1. Schematic representation of a honeycomb monolith catalyst [15]. process [5,9,12].
114 V. Tomašić, F. Jović / Applied Catalysis A: General 311 (2006) 112–121

Every decision about the use of ceramic monolith catalysts Table 2

Physical data of ceramic and metal substrates for 400 cpsi monolith catalyst
must take into consideration their disadvantages which are
[55]
generally [1,11,12]:
Monolith support (cpsi) Ceramic 400 Metallic 400
(a) in the ceramic monoliths with almost nonporous walls of Wall (foil) thickness (mm) 6.5 2.0
the channels the radial mass transfer between adjacent Geometric surface area (m2 l
1) 2.8 3.7
channels is very limited and the radial heat transfer occurs Thermal mass at 200 8C (J kg
1 K
1) 699 490
Open frontal area (%) 75.0 89.3
only by conduction through the solid walls;
Pressure loss (%) 130 100
(b) due to low thermal conductivity ceramic monoliths are
operated at nearly adiabatic conditions;
(c) the risk of cracking of the ceramic monolith structure under 1.1.3. Development and application of monolith structures
conditions of rapidly changing temperatures; Development and application of monolith structures have
(d) basic design and preparation of monolithic catalysts, versus been triggered by many problems encountered with hetero-
conventional ones, is more complex and costly (this geneous catalytic processes, e.g. in a fixed bed reactor, slurry
disadvantage equally refers to ceramic and metallic reactor and other multiphase reactors [1,12,29,30]. It is known
monolith catalysts). that in heterogeneous catalytic reactions the catalyst should
preferably have high surface area. This surface area usually
The advantages of metallic over ceramic monoliths are: increases with decrease of the catalyst particles, but this may
cause significant pressure drop through the catalytic layer in the
(a) very thin metallic walls (approximately 0.04–0.05 mm) reactor. Sometimes, it does not pose a major problem if, for
present only minimal resistance to the exhaust gases, example, a heterogeneous catalytic reaction is slow and requires
preventing the accumulation of significant backpressure; high residence time of the reactant in the catalytic layer. In that
(b) high thermal conductivity in the metal material allows more case, low flow rate of the reaction mixture does not cause
rapid attainment of the necessary operating temperature and significant pressure drop. On the other hand, for the fast chemical
minimizing of pollutant emission during the cold start reaction, which occurs under conditions of high reactant flow
phase; rates, high surface area of the catalyst is necessary. This leads to
(c) better mechanical durability; the problems with pressure drop in the fixed bed reactor. It is
(d) lower overall volume and load; important to point out that pressure drop is related both to the
(e) additional design freedom over ceramic monoliths (differ- particle size of the catalyst as well as to its shape and packing in
ent basic shapes and channel size, conical configuration, the catalytic layer. In the multiphase systems, e.g. in gas–liquid–
additional structuring within the channels and provision of solid reacting systems, additional problems arise, such as mass
‘‘passive channels’’ for metallic monoliths, which sig- transfer limitations in the gas–liquid interphase, in the liquid film
nificantly improve turbulence and enhance heat and mass surrounding the catalyst and in the solid phase, i.e. in the porous
transfer) [1,13,27,28]. catalytic layer. In the so complex systems hydrodynamics is also
a key factor. It is a known fact that concentration of species which
A disadvantage of metallic monoliths is their limited thermal diffuse from the fluid (gas, liquid) to the surface of the second
stability at the temperatures over 1573 K (due to melting, phase is changed the most near the interface between the phases.
corrosion, etc.) which is not the case with ceramic monoliths This leads to appearance of concentration gradient in the
[11,12,15]. The amount of catalyst on the walls in a given boundary layer (film). The thickness of this boundary layer is
volume of metallic monolith is much less than a comparable determined by hydrodynamics. Consequently, intensively mix-
volume of ceramic monolith. Therefore, for chemical ing of the phases or increasing the flow rate of the fluid leads to
controlled reactions the metallic monoliths are not well suited. the improved mass transfer. In line with this, it is important to
The main differences between properties of metallic and emphasize that under specific operating conditions ‘‘segmented
ceramic monoliths are shown in Tables 1 and 2. flow’’ might occur in the monolith reactors [1,8,29,30]. This type
of flow, which is also called Taylor flow or slug flow, can be
Table 1 explained in the following way: liquid slugs well separated by gas
Comparison of ceramic and metallic monolith catalyst properties slugs (bubbles), flow consecutively through the monolith
Property Monolith channels. Such flow enables good recirculation within the liquid
Ceramic Metallic
slugs and provides only a thin liquid film between the gas slugs
and the channel walls. Because of this, the rate of mass transfer is
Specific surface area +

very large. With regard to previous considerations, it can be
Heat transfer
+
Pressure drop
+ concluded that monolith reactors have great potentials in two-
Porosity +
component systems, and especially in three-component systems.
Mechanical stability
+ Table 3 shows advantages of monolith reactors over slurry and
Thermal stability +
trickle-bed reactors [11,30]. A distinctive feature of the monolith
Wall thickness
+
reactors, compared to other multiphase reactors, is in that the
Overall volume
+
monoliths do not display usual difference between the reactor
 V. Tomašić, F. Jović / Applied Catalysis A: General 311 (2006) 112–121 115

and catalyst particles with respect to the action level (i.e. Ceramic monoliths with porous walls are prepared by the
consideration of reactor at the meso-scale versus catalyst addition of appropriate polymers (e.g. polyurethanes, Nafion-
particles at the micro-scale) [4–7]. Therefore, the both terms, e.g. H: perfluorosulfonic acid/PTFE copolymer in H+ form, etc.) to
monolith catalyst and monolith reactor can be used with the same the starting mixture for ceramic preparation [1,31,51]. In later
meaning. stages (drying and oxidation) performed at high temperatures
the polymer is removed, thus giving the required macroporous
2. Preparation of monolithic catalysts structure.

2.1. Ceramic monoliths 2.2. Metallic monoliths

As shown in Fig. 1, ceramic monolith structure has many Development of metallic monoliths started in the 1960s,
straight and, usually, parallel channels. Commonly, such mostly for the needs of chemical industry. In the 1980s their use
structures are obtained by extrusion in specially designed in the cleanup of the vehicles exhaust gases came under
devices (extruders) [11,16,31–37], and less frequently by consideration.
corrugation [38–40]. Extrusion most often applies various Metallic monoliths are almost exclusively obtained by
clays, the precursors of starting materials, binders and additives, corrugation (flexing) of flat and corrugated metal plates and/or
relevant to the desired type of ceramic [1,11,16,31]. Cordierite bends [16,52]. Thin metal plates or bends are frequently made of
(2MgO2Al2O35SiO2) is, together with alumina, the most iron alloys, usually with small amounts of aluminum. Oxidation
common material for monolith extrusion [32]. More than 90% of of aluminum produces a layer of aluminum oxide important for
all monolith catalysts used for the cleanup of exhaust gases good adhesion of the second oxide layer, applied at later
from cars are of cordierite ceramic. Other materials such as preparation stages as the support to a catalytically active
SiC, B4C, Si3N4, BN, AlN, TiO2, ZrO2, ZrSiO4, ZrB2, mullite component [53]. Metallic monoliths are usually made of stainless
(3Al2O32SiO2), Al titanate (Al2O3TiO2), Li-Al silicate steel and the material under the trademark of Fecralloy1 (73%
(LiO2Al2O34SiO2) and others are less common and some of Fe, 15–20% Cr, 5% Al, rare metals in traces) [12,16]. Johnson
them are more expensive [16,33]. Corning [41], Cormetech [42], Matthey [54], Emitec [55], Grace [56] and others are the most
NGK [43], Engelhard [44], Steuler Gmbh [45] and KWH [46] famous manufacturers of metallic monoliths.
are just some of the leading manufacturers of ceramic monoliths.
The details about preparation of ceramic monolith structures 2.3. Application of the secondary support to the monolith
can be found mostly in the patent literature [32,34–39] and in a structure
few works published in the scientific–technical publications
[11,14,16,33]. Merkel and Murtagh [34] describe preparation Specific surface of the ceramic and metallic monolith
of cordierite monoliths which comprises the following steps: support is very small (of the cordierite ceramic monolith it is ca.
(a) preparation of the starting mixture of talc, clay and other 2 m2 g
1). Therefore, primary support (the monolith) has to be
materials containing Al and Si; (b) mixing and bringing of the coated with the secondary support, usually a layer of the porous
mixture into the state suitable for shaping; (c) shaping by metallic oxide (such as Al2O3, TiO2, mixture of oxides, etc.).
extrusion; (d) drying; and (e) thermal treatment (drying, This can be done by various methods of which the washcoating
calcination and sintering) at 1473–1773 K. is the commonest one [11]. Coating of the monolith surface
Properties of the extruded ceramic monolithic catalyst with the oxide requires the solution or colloid suspension with
depend on the type and properties of the starting materials, precursor(s) of one or more oxides (precursor is in the form of
additives, pH, the water content and pressure used in extrusion suspended particles). In some instances the sol–gel method is
[14,16,31]. The additives are celluloses, CaCl2, ethylene, applied, where the liquid phase contains secondary support
glycols, diethylene glycols, alcohols, paraffins, heat-resistant precursors. This is achievable by hydrolytic procedure based on
inorganic fibers, etc. [16,37] and are used to enhance the hydrolysis of the appropriate alkoxides in the presence of either
resistance to temperature shocks [36], better porosity and acid or base, followed by polycondensation in the next step:
adsorbability [37], and to improve mechanical properties [11].
In addition to water, other solvents can be used as well, e.g. MðORÞn þ nH2 O ! MðOHÞn þ nROH;
ketones, alcohols and ethers [16,37]. M ¼ Al; Si; Ti; Zr; . . . (1)
Besides the aforementioned procedure for preparation of
cordierite ceramic, which comprises calcination of the
M
OH þ HO
M0
!
M
O
M0
þ H2 O (2)
mixture of clay, talc and other components with Al and or by non-hydrolytic sol–gel procedure:
Si, there is a sol–gel method [47–50]. Its advantages over the
previous one are in the resulting high-purity cordierite MOR þ MX ! intermediates ! M
O
M þ RX (3)
ceramic (attributed to higher purity of the starting materials)
of a strictly defined microstructure, adjustable homogeneity So prepared sol is applied to the basic monolith structure
on the atomic level, possibility of carrying out the process at mostly by ‘‘dipping technique’’ [11]. After a predefined time,
lower temperatures (ca. 1273 K), addition of various excess sol is removed from the monolith, which is then dried
components at one step only, etc. and calcinated.
116 V. Tomašić, F. Jović / Applied Catalysis A: General 311 (2006) 112–121

Al-sol can be prepared with various aluminum precursors, 3. Application of monolithic catalysts
e.g. pseudo-boehmite, AlO(OH)xH2O, aluminum alkoxide,
etc. Additives, such as urea or organic amines (e.g. 3.1. Upgraded procedures for pollution abatement from
hexamethylenetetramine, HMT) are used as quality improvers non-stationary and stationary sources
of Al2O3 layer [16]. Decomposition of additives at high
temperatures (calcination) (Eq. (4)) gives this layer the required The commonest application of monolithic catalysts and
porosity. reactors is in abatement of pollution from non-stationary
sources (treatment of exhaust gases from cars and other
NH2 CONH2 þ H2 O ! 2NH3 þ CO2 (4)
vehicles, decomposition of ozone in aircrafts, etc.) and from
Additives have the influence on the stability of the sols as well. stationary sources (selective reduction of NOx, destruction of
Similarly, addition of the sintering-inhibiting cations (e.g. Ba2+, volatile organic compounds (VOC), catalytic combustion).
La3+, Mg2+, Zr4+ and Si4+) which inhibit conversion of g-Al2O3 More details about commercial application of monolith
into the inert a-phase (at temperatures >1273 K), provides structures in the above processes can be found in the literature
higher resistance of alumina to sintering at high temperatures. [1,13,24,25,28,66–68]. Here, particular focus is on the less
It is a known fact that metals unlike ceramics have known applications of monolithic catalysts and reactors. This
significantly higher thermal expansion coefficient. Therefore, covers application of metallic monoliths, i.e. of specially
during application of an appropriate support of a catalytically constructed monolithic catalysts in abatement of pollution
active component to the metallic monolith base, adhesion of during cold start of the motors and the use of the so-called
such a layer requires particular attention [11,16]. Various ceramic and/or catalytic filters in the treatment of exhaust and
thermal, chemical and electrochemical procedures are available flue gases from stationary and non-stationary sources.
for this purpose and they are usually preceded by metal surface The first monolithic catalysts used in the treatment of
oxidation. exhaust gases from cars had ceramic monolith structure (mostly
cordierite) with Al2O3 layer as the support to a catalytically
2.4. Incorporation of active phase into the monolith active component and with the mixture of precious metals (Pt–
Pd–Rh). Subsequently, however, it was found out that catalyst
One or more catalytically active components are applied to efficiency depends on the motor operation. Actually, the
the secondary support using the methods that are basically very efficiency is very low during cold start when also more than
similar to the conventional ones in catalyst preparation. These 80% of total emissions are generated. This is attributed to poor
are: impregnation, adsorption, ion exchange, (co)precipitation, thermal conduction of ceramic. Therefore, satisfactory operat-
deposition-precipitation, sol–gel method, slurry dip-coating ing temperature (ca. 523–623 K) of ceramic monolith catalysts
and ‘‘in situ’’ crystallization (if a monolith with appropriate is achieved after some time of motor operation and only then
zeolite as a catalytically active component is to be obtained) they exhibit satisfactory activity [27,28]. In order to overcome
[11,16]. Other steps in preparation of a monolithic catalyst, e.g. this problem Emitec [55], one of major world metallic monolith
drying, calcination and reduction are not different from the manufacturers, developed the treatment system for exhaust
conventional ones in catalyst preparation. Therefore, they are gases generated by unleaded gasoline. The system has two
not discussed in this section. parts: (a) metallic monolith preheater, i.e. electrically heated
In some cases it is possible to apply secondary support and a catalytic converter (EHC) and (b) basic ceramic monolith
catalytically active component simultaneously, or to add a catalyst. The electrically heated converter (Fig. 2) is installed
catalytically active component to the starting extrusion mixture adjacent to the entry to basic ceramic catalytic converter. This
[57,58]. However, it is worthy of mention that extrusion is a design reduces emissions during cold start, thus contributing to
complex method where rheological properties of the extrusion increase of the catalyst overall efficiency [52,55].
mixture are very important [57]. In addition, active phase might Ceramic wall flow filters enable removal of solid particles
be sintered during sintering, ending up in disturbed micro- and (fly ashes, dust, soot, etc.) from waste gases. Their commonest
mesoporosity of the final product [16].
Recently, ceramic industry has applied state-of-the-art
techniques for preparation of ceramic materials for special
use, such as spin-coating [59], chemical vapor deposition
(CVD) [60,61], chemical vapor infiltration (CVI) [62], heat
spraying [63,64], etc. Deposition can be carried out by
convectional heating, with laser or microwave drying. It has
been shown that microwave drying is of great practical use
because the method is fast and enables homogeneous
distribution of the active phase in the catalyst [65]. As
expected, results of the research in materials, especially those
focused on products development (e.g. integral components and
composites) will significantly contribute to further develop-
ment, production and application of monolithic catalysts [16]. Fig. 2. Electrically heated catalytic converter [55].
 V. Tomašić, F. Jović / Applied Catalysis A: General 311 (2006) 112–121 117

or soot accumulate. Furthermore, reaction between the accumu-

lated soot and NO2 (generated in the first part of the filter) causes
oxidation of soot, which enables continuous auto-regeneration of
the filter. Regeneration is carried out below 523 K. As already
mentioned, the conventional ceramic filters are regenerated
(without NO2 as an oxidant) at considerably higher temperatures.
Fig. 3. Ceramic filters for flue gas cleaning [72].
3.2. Potential application of monoliths
application is in the treatment of the flue gases from stationary
sources (waste incinerators, fluidized-bed coal combustors, 3.2.1. Catalytic fuel combustors in the systems with gas
diesel engines, etc.). In some cases wall channels of ceramic turbines
monoliths may contain a catalytically active component(s) (e.g. In addition to already mentioned processes, applied in
V2O5, V2O5-TiO2, V2O5-Al2O3, etc.) that enables simultaneous abatement of pollution from stationary and non-stationary
oxidation and/or reduction of other pollutants from the exhaust sources and based on the ‘‘end of pipe’’ approach, monolith
gas (VOCs, CO, SO2, NOx, etc.). Therefrom it appears that the structures are important in the prevention of air pollution. This
use of the so-called catalytic filters enables simultaneous applies to gas turbines with catalytic combustor systems. The
physical separation of suspended solid particles and catalytic literature contains many scientific and technical works dealing
removal of gaseous pollutants. As stated in the introductory with this issue [25,33,53,74–78].
part, the main advantage of such integrated systems is in a Comparison between the conventional (non-catalytic) and
decreased number of process units, saved space and energy and, catalytic fuel combustors is shown in Fig. 5 [78]. In the
consequently, reduced overall process operation costs. Appli- conventional system compressed air is preheated to 573–673 K,
cation of a catalytic filter in the so-called SOx-NOx-Rox Box mixed with fuel and drawn into combustion chamber.
process and in similar processes is described in the patents Combustion of the fuel–air mixture might produce at the
[69,70]. chamber outlet the temperature as high as 2273 K. This requires
Ceramic filters are also used for cleanup of the exhaust gases introduction of cold air into combustion mixture before it
generated by combustion of motor diesel fuels [71]. Here, reaches the turbine paddles (optimal temperature at the turbine
usually one half of all monolith channels is closed on one side inlet is 1373–1573 K, due to thermal stability of the
and other half is closed on the reverse side (Fig. 3) [13,72]. Such construction materials). On the other hand, the catalyst reduces
configuration causes agglomeration of solid particles within the activation energy necessary for combustion reactions. There-
channels, while the remaining gases, free of solid particles, pass fore, with the catalyst present, complete combustion of the
by diffusion through the wall into neighboring channels. When fuel–air mixture can occur at significantly lower temperatures,
specific saturation level of ceramic filter with solid particles is which is not so with the systems providing homogeneous
achieved, regeneration has to be performed. Regeneration is combustion in the gaseous phase (1373–1573 K versus 2073–
usually done by oxidation of the generated soot particles at high 2273 K). The advantages of catalytic combustors are in that
temperatures (ca. 720 K). Sometimes this process needs they prevent generation of ‘‘thermal’’ NOx (generated mostly at
addition of a homogeneous catalyst (e.g. organometallic
compounds Cu, Ni, Ce, Mo, Fe, etc.) to the diesel fuel so as
to prevent excessive heating during regeneration with
consequent melting of the filter [13,72].
Problem related to simultaneous removal of solid particles and
nitrogen oxides from the exhaust gases generated by diesel fuel
combustion and regeneration of a catalytic filter, used in this
system, has been overcome only recently, by development of
continuously regenerating filters (CRTTM) [21,28,73] (Fig. 4).
They work in the following way: the first part of the filter has a
ceramic monolith catalyst (Pt as a catalytically active component)
that enables oxidation of CO and hydrocarbon into CO2 and H2O,
respectively. Simultaneously, nitrogen oxides (present in flue
gases mostly as NO) oxidize to NO2, while the remaining gas
mixture passes through other part of the filter where solid particles

Fig. 5. (a) Conventional (non-catalytic) and (b) catalytic combustor in an open-

Fig. 4. Simplified schematic diagram of a continuously regenerating filter [28]. cycle gas turbine [78].
118 V. Tomašić, F. Jović / Applied Catalysis A: General 311 (2006) 112–121

T > 1673 K), they do not require temperature decrease of the Relevant to the mode of gas and/or liquid passage through
gaseous mixture at the outlet of combustion chamber, they the monolith reactor, the operation is either co-current or
reduce constraints related to thermal stability of the construc- counter-current. With respect to the relatively small channel
tion materials, etc. [74–76]. diameter, usual for monolith structures, counter-current
Monolithic catalysts are used to ensure necessary conditions operation is very limited and applies to the internally finned
for catalytic combustion (e.g. high specific surface of the catalyst monoliths [87]. In most cases solid phase is immovable but
and simultaneous insignificant pressure drop through the there are designs with the moving bed application [1].
catalytic layer). To date research in catalysts development has Generally, monolith reactors are multifunctional reactor
been conducted with ceramic and metallic monoliths that contain systems with the following key properties: efficient contact of
mostly Al2O3 as a secondary support, modified by the addition of the reactants with (most frequently) solid catalyst and
Ba, La, Si and other elements to stabilize and improve chemical, avoidance of problems related to partial wetting of the catalyst
thermal and other properties. The commonest catalytically active with liquid phase; possibility of combining reaction and
components are precious metals (Pt and Pd), oxides of transition separation processes; possibility of the controlled reactants
metals, complex oxides (spinels-oxides type AB2O4, e.g. loading and products removal, etc. The aforementioned implies
MgAl2O4; perovskite-oxides type ABO3, e.g. LaCoO3, etc.) that with monolith reactors one can combine the advantages of
and various hexa-aluminates and substituted hexa-aluminates conventional multiphase reactors (e.g. slurry and trickle-bed
(BaO6Al2O3, etc.) [33,74,78]. However, so far studied catalysts reactors) under simultaneous removal of their disadvantages
are still lacking satisfactory stability and life at the temperatures (Table 3). This increases process efficiency and its cost-
of 1373–1773 K [66,74,78]. This necessitates further studies effectiveness. One of disadvantages of monolith reactors,
focused on upgrading of the catalyst thermal stability and however, is poor distribution of liquid and/or gas along the
stability in the presence of water steam, oxygen and other reactor’s cross-section. This fact makes their use difficult,
components (S, As and Pb) as well as simultaneous compliance especially under higher flow rates. The attempts are being made
with continuous operation for at least 1 year (ca. 8000 h). to resolve the problem by changing geometry at the entry to the
Zwinkels et al. [74] and Thevenin et al. [78] state that the monolithic structure and with other constructional designs [87].
problems related to unsatisfactory activity and thermal stability Irrespective of many advantages over other types of
of the catalyst under mentioned conditions can be partially multiphase reactors, there is only one example of commercial
settled with a hybrid combustion system, i.e. variously designed application of monolithic catalysts in multiphase processes. It
combustion chambers that enable controlled loading of the is hydrogenation of alkyl anthraquinone in the production of
secondary fuel and/or air, and with a multilayer monolithic hydrogen peroxide [82,88,89]. Other potential applications are
catalyst in the combustion chamber, etc. considered in the context of laboratory- and semi-industrial
scale. The following are just some of the potential areas of
3.2.2. Substitution for multiphase reactors application: hydrogenation of a-methyl styrene to cumene
Substitution of conventional multiphase reactors for mono- [90], hydrogenation of dinitrotoluene to toluenediamine [91],
lith reactors has been the matter of consideration over past 15 hydrogenation of benzaldehyde to benzylalcohol [92] and
years, especially in processes of hydrogenation in the liquid other selective hydrogenations and oxidations [93], biocata-
phase [79–82], oxidation of organic and inorganic compounds lyzed reactions, etc. The details about potential applications of
in aqueous solutions (e.g. waste waters) [83] and in biochemical monolith reactors in chemical industry are given in the
processes [84–86]. Often the catalyst is a solid phase (or a living literature [1,30,33,94]. The use of ceramic and/or metallic
organism immobilized in the solid monolith support) while monoliths is also investigated within the studies of hydrogen
other reaction components can be in gaseous and/or liquid state generation, related to the development and use of fuel cells
[1,29,30]. For example, various combinations of reaction [94].
phases are acceptable: gas–solid; liquid–solid; gas–liquid– Monolith catalyst can be also used for Fischer-Tropsch
solid; liquid–liquid–solid; and gas–liquid–liquid–solid. (FT) synthesis. The development of new materials and of

Table 3
Comparison of multiphase reactors
Property Monolith reactor Slurry reactor Trickle-bed reactor
Energy input Low Medium, stirring High, pressure drop
Catalyst efficiency High, thin active layer High, small particles Low, large particles
required due to pressure drop
Pressure drop Insignificant Small High
Catalyst separation Unnecessary Costly filtering necessary Easy
Catalyst loading Medium or small Medium or small High
Catalyst replacement Difficult Easy, continuous exchange Difficult
during operation
Experience Two phases-extensive High High
multiphase-limited
 V. Tomašić, F. Jović / Applied Catalysis A: General 311 (2006) 112–121 119

reactor configurations may lead to improvements in reactor 4. Outlook and research priorities
productivity and process economics. The developed Fischer-
Tropsch reactor systems have included conventional fixed- Many literature references state that development of
bed, three-phase slurry bubble column designs, fluidized and/ monolithic catalysts and/or reactors has been one of major
or moving bed, and monolith reactor. Due to the complicated achievements in the field of heterogeneous catalysis and
interplay between heat and mass transfer and the relatively catalytic reaction engineering. According to expectations,
high cost of Fischer-Tropsch catalysts, no single reactor monoliths will have increasing applications in chemical and
design has dominated the recent commercial development biochemical processes, in mass production of chemicals and
efforts. The field of monolith application in FT synthesis is production of fine chemicals and specialty chemical products,
very active in research [98–109]. Different applications of in catalytical and non-catalytical treatment of fuel and flue
monolith reactors have been proposed for FT synthesis in gases, in catalytical combustion of fuel and other multiphase
recent literature. processes in chemical industry [1,14,95–97,115–117].
Monolithic catalysts for FT synthesis consist of long parallel Obviously, materialization of these expectations requires
channels (0.5–3 mm internal diameter) separated by thin walls further research that should, also, enable achievement of the
(0.1–0.3 mm) [101]. The walls can be either made of cordierite following goals:
on which a high surface area catalyst support can be wash coated
or of a suitable catalyst support such as alumina and silica. The  Development of the existing and new procedures for
active metals, which are included with or applied to the support, preparation of the monolithic catalysts taking into account
may include metals or combination of metals such as cobalt process economics; upgrading of catalytical and physical
[99,100,102–104,109], iron [107,109], copper [106,109], nickel properties (optimizing of chemical composition, structure,
[106,109], platinum [100,109], rhenium [99,102,103,109] and porosity and distribution of a catalytically active compo-
ruthenium [109]. Monolithic reactors usually work in a nent(s), etc.) and improvement of mechanical, thermal and
temperature regime from room temperature [109], 188– other properties determining practical use of the monolithic
194 8C [100], up to 240 8C [102,107]. Synthesis gas composi- catalysts/reactors.
tions are from stoichiometrically excess carbon monoxide to  Better distribution of fluids along the cross-section of a
excess hydrogen (H2/CO = 1–3) [98,100,102,107]. monolith reactor in multiphase systems and development of
The configuration of monolith reactor, where the heat can be corresponding mathematical models that describe fluid
removed by recycling liquid through the channels of the dynamics and complex processes performed in these systems.
monolith and an external heat exchanger is the basis of the Optimization of the monolith reactor operation requires
monolithic loop reactor (MLR). Experimental results for this integral approach to the catalyst and reactor design. This
type of monolith reactor show the potential application for FT approach is based on considering the catalyst in its multi-
synthesis [99–103,108]. Examples of possible configurations scale components at the same time, which include active
of the monolith loop reactor can be found in the literature sites, solid architecture and texture, nano- and macro-
[108]. structure.
In the literature can be found more information about some Application of the basic methodology of chemical engineering
other interesting aspects of monolith reactors application, e.g. and results of research and developments in the field of
heat transfer [110–112], and comparisons with other type of materials science will play important role in the achievement of
reactors [113,114]. the above goals.
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