Professional Documents
Culture Documents
The first major breakthrough in industrial the discovery by FISCHER and TROPSCH [11] of the
catalysis was the synthesis of ammonia from synthesis of hydrocarbons and oxygenated com-
the elements, discovered by HABER [3,6,7] in pounds from CO and H2 over an alkalized iron
1908, using osmium as catalyst. Laboratory catalyst. The first plants for the production of
recycle reactors for the testing of various am- hydrocarbons suitable as motor fuel started up in
monia catalysts which could be operated at high Germany 1938. After World War II, Fischer-
pressure and temperature were designed by Tropsch synthesis saw its resurrection in South
BOSCH [3]. The ammonia synthesis was com- Africa. Since 1955 Sasol Co. has operated two
mercialized at BASF (1913) as the Haber – plants with a capacity close to 3 106 t/a.
Bosch [8] process. MITTASCH [9] at BASF devel- One of the highlights of German industrial
oped and produced iron catalysts for ammonia catalysis before World War II was the synthe-
production. sis of aliphatic aldehydes by ROELEN [12] by
In 1938 BERGIUS [3,10] converted coal to the addition of CO and H2 to olefins in the
liquid fuel by high-pressure hydrogenation in presence of Co carbonyls. This homogeneous-
the presence of an Fe catalyst. ly catalyzed reaction was commercialized in
Other highlights of industrial catalysis were 1942 by Ruhr-Chemie and is known as Oxo
the synthesis of methanol from CO and H2 over Synthesis.
ZnO – Cr2O3 and the cracking of heavier pe- During and after World War II (till 1970)
troleum fractions to gasoline using acid-activat- numerous catalytic reactions were realized on
ed clays, as demonstrated by HOUDRY [3,6] in an industrial scale (see also Chapter Applica-
1928. tion of Catalysis in Industrial Chemistry).
The addition of isobutane to C3 – C4 olefins Some important processes are compiled in
in the presence of AlCl3, leading to branched Table 1.
C7 – C8 hydrocarbons, components of high- Table 2 summarizes examples of catalytic
quality aviation gasoline, was first reported by processes representing the current status of the
IPATIEFF et al. [3,7] in 1932. This invention led to chemical, petrochemical and biochemical in-
a commercial process of UOP (USA). dustry as well as the environmental protection
Of eminent importance for Germany, which (see also Chapter Application of Catalysis in
possesses no natural petroleum resources, was Industrial Chemistry).
Table 1. Important catalytic processes commercialized during and after World War II (until 1970) [13,14]
1971 – 1980 automobile emission control Pt – Rh – CeO2 – Al2O3 removal of NOx, CO, CHx
(three-way catalyst)
carbonylation (Monsanto process) organic Rh complex acetic acid from methanol
MTG (Mobil process) zeolite (ZSM-5) gasoline from methanol
1981 – 1985 alkylation (Mobil – Badger) modified zeolite (ZSM-5) ethylbenzene from ethylene
selective catalytic reduction (SCR; V Ti (Mo, W) oxides reduction of NOx with NH3 to N2
stationary sources) (monoliths)
esterification (MTBE synthesis) ion-exchange resin methyl-tert-butyl ether from
isobutene þ methanol
oxidation (Sumitomo Chem., 1. Mo, Bi oxides acrylic acid from propene
2-step process) 2. Mo, V, PO (heteropolyacids)
oxidation (Monsanto) vanadylphosphate maleic anhydride from n-butane
fluid-bed polymerization (Unipol) Ziegler – Natta type polyethylene and polypropylene
hydrocarbon synthesis (Shell) 1. Co – (Zr,Ti) – SiO2 middle distillate from CO þ H2
2. Pt – SiO2
environmental control Pt – Al2O3 (monoliths) deodoration
(combustion process)
1986 – 2000 oxidation with H2O2 (Enichem) Ti silicalite hydroquinone and catechol
from phenol
hydration enzymes acrylamide from acrylonitrile
ammoxidation (Montedipe) Ti silicalite cyclohexanone oxime from
cyclohexanone, NH3, and H2O2
dehydrogenation of C3, C4 alkanes Pt(Sn) – zinc C3, C4 olefins
(Star and Oleflex processes) aluminate,
Pt – Al2O3
2000 – catalytic destruction of N2O from Fe zeolite removal of nitrous oxide
nitric acid tail gases (EnviNOx
process, Uhde)
HPPO (BASF-Dow, Ti silicalite propylene from propene
Degussa-Uhde)
2. Theoretical Aspects day) and as high as 109 s1 (gas kinetic collision
rate at 1 MPa) are observed.
The classical definition of a catalyst states It is plausible that it is extremely difficult, if
that “a catalyst is a substance that changes the not impossible, to describe the catalytic phe-
rate but not the thermodynamics of a chemical nomenon by a general theory which covers the
reaction” and was originally formulated by entire range of reaction conditions and observed
OSTWALD [4]. Hence, catalysis is a dynamic site-time yields (reaction rates). However, there
phenomenon. are several general principles which are consid-
As emphasized by BOUDART [19], the condi- ered to be laws or rules of thumb that are useful
tions under which catalytic processes occur on in many situations. According to BOUDART [19],
solid materials vary drastically. The reaction the value of a principle is directly related to its
temperature can be as low as 78 K and as high generality. In contrast, concepts are more spe-
as 1500 K, and pressures can vary between 109 cialized and permit an interpretation of phenom-
and 100 MPa. The reactants can be in the gas ena observed for special classes of catalysts or
phase or in polar or nonpolar solvents. The reactions under given reaction conditions.
reactions can occur thermally or with the assis- In this chapter, important principles and
tance of photons, radiation, or electron transfer concepts of heterogeneous catalysis are dis-
at electrodes. Pure metals and multicomponent cussed, followed by a section on kinetics
and multiphase inorganic compounds can act as of heterogeneously catalyzed reactions. The
catalysts. Site-time yields (number of product chapter is concluded by a section on the deter-
molecules formed per site and unit time) as low mination of reaction mechanisms in heteroge-
as 105 s1 (corresponding to one turnover per neous catalysis.
8 Heterogeneous Catalysis and Solid Catalysts
DE ¼ a Dq;
where DE is the decrease in activation energy Figure 1. Volcano plot for the decomposition of formic
corresponding to an increase Dq in the heat of acid. The temperature T at which the rate of decomposition v
has a fixed value is plotted against the heat of formation DHf
reaction. Hence, an elementary step will have a of the metal formate (adopted from [31]).
high rate constant in the exothermic direction
when its heat of reaction q increases. Since the
activation barrier in the endothermic direction is metal formates were chosen as the measure of
equal to the sum of the activation energy E and the stability of the intermediate. At low values of
the heat of reaction, the rate constant will de- DHf, the reaction rate is low and corresponds to
crease with increasing q. the rate of adsorption, which increases with
The Brønsted relationship represents a bridge increasing heat of formation of the bulk for-
between thermodynamics and kinetics and, to- mates (representing the stability of the surface
gether with the Sabatier principle, permits an compound). At high values of DHf the reaction
interpretation of the so-called volcano plots first rate is also low and corresponds to the desorp-
reported by BALANDIN [20]. These volcano curves tion rate, which increases with decreasing DHf.
result when a quantity correlated with the rate of As a consequence, a maximum in the rate of
reaction under consideration is plotted against a reaction (decomposition of formic acid) is ob-
measure of the stability of the intermediate served at intermediate DHf values which is
compound. The latter quantity can be the heat neither a pure rate of adsorption nor a pure rate
of adsorption of one of the reactants or the heat of of desorption but which depends on both.
formation of a bulk compound relative to the
surface compound, or even the heat of formation
of any bulk compound that can be correlated with 2.1.2. The Principle of Active Sites
the heat of adsorption, or simply the position of
the catalytic material (metal) along a horizontal The Sabatier principle of an unstable surface
series in the Periodic Table [263]. intermediate requires chemical bonding of re-
As an example, Figure 1 shows the volcano actants to the catalyst surface, most likely be-
plot for the decomposition of formic acid on tween atoms or functional groups of reactant
transition metals [21]. The intermediate in this and surface atoms. This leads to the principle of
reaction was shown to be a surface formate. active sites. When LANGMUIR formulated his
Therefore, the heats of formation DHf of the bulk model of chemisorption on metal surfaces [22],
Heterogeneous Catalysis and Solid Catalysts 9
he assumed an array of sites which were energet- inequivalent active sites, BOUDART et al. [29]
ically identical and noninteracting, and which coined the terms structure-sensitive and struc-
would adsorb just one molecule from the gas ture-insensitive reactions. A truly structure-in-
phase in a localized mode. The Langmuir adsorp- sensitive reaction is one in which all sites seem
tion isotherm results from this model. The sites to exhibit equal activity on several planes of a
involved can be considered to be active sites. single crystal. Surprisingly, many heteroge-
LANGMUIR was already aware that the as- neously catalyzed reactions turned out to be
sumption of identical and noninteracting sites structure-insensitive. Long before experimental
was an approximation which would not hold for evidence for this phenomenon was available and
real surfaces, when he wrote [23]: “Most finely before a reliable interpretation was known,
divided catalysts must have structures of great TAYLOR predicted it by writing [24]: “The
complexity. In order to simplify our theoretical amount of surface which is catalytically active
consideration of reactions at surfaces, let us is determined by the reaction catalyzed.” In
confine our attention to reactions on plane sur- other words, the surface of a catalyst adapts
faces. If the principles in this case are well itself to the reaction conditions for a particular
understood, it should then be possible to extend reaction. The driving force for this reorganiza-
the theory to the case of porous bodies. In tion of a catalyst surface is the minimization of
general, we should look upon the surface as the surface free energy, which may be achieved
consisting of a checkerboard.” LANGMUIR thus by surface-reconstruction [30,31]. As a conse-
formulated the surface science approach to het- quence, a meaningful characterization of active
erogeneous catalysis for the first time. sites requires experiments under working (in
The heterogeneity of active sites on solid situ) conditions of the catalytic system.
catalyst surfaces and its consequences were The principle of active sites is not limited to
emphasized by TAYLOR [24], who recognized metals. Active sites include metal cations, an-
that “There will be all extremes between the ions, Lewis and Brønsted acids, acid – base
case in which all atoms in the surface are active pairs (acid and base acting simultaneously in
and that in which relatively few are so active.” In chemisorption), organometallic compounds,
other words, exposed faces of a solid catalyst and immobilized enzymes. Active sites may
will contain terraces, ledges, kinks, and vacan- include more than one species (or atom) to
cies with sites having different coordination form multiplets [20] or ensembles [32]. A
numbers. Nanoscopic particles have edges and mandatory requirement for these sites to be
corners which expose atoms with different co- active is that they are accessible for chemisorp-
ordination numbers [25]. The variation of coor- tion from the fluid phase. Hence, they must
dination numbers of surface atoms will lead to provide free coordination sites. Therefore,
different reactivities and activities of the corre- BURWELL et al. [33,34] coined the term coordi-
sponding sites. In this context, Schwab’s adli- natively unsaturated sites in analogy with ho-
neation theory may be mentioned [26], which mogeneous organometallic catalysts. Thus, ac-
speculated that one-dimensional defects con- tive sites are to be considered as atoms or groups
sisting of atomic steps are of essential impor- of atoms which are embedded in the surface of a
tance. This view was later confirmed by surface matrix in which the neighboring atoms (or
science studies on stepped single-crystal metal groups) act as ligands. Ensemble and ligand
surfaces [27]. effects are discussed in detail by SACHTLER [35]
In addition to variable coordination numbers and quantum chemical treatments of geometric
of surface atoms in one-component solids, the ensemble and electronic ligand effects on metal
surface composition may be different from that alloy surfaces are discussed by HAMMER and
of the bulk and different for each crystallogra- NøRSKOV [36].
phic plane in multicomponent materials (surface
segregation [28]). This would lead to a hetero-
geneity of the local environment of a surface 2.1.3. Surface Coordination Chemistry
atom and thus create nonequivalent sites.
Based on accurate kinetic measurements The surface complexes formed by atoms
and on the Taylor principle of the existence of or molecules are now known to usually
10 Heterogeneous Catalysis and Solid Catalysts
Figure 3. Site-isolation principle. Schematic of lattice oxygen arrangements on hypothetical surfaces. Anticipated reaction
paths of propene upon contact with these surfaces (NR ¼ no reaction; adopted from [62])
state is the transalkylation of m-xylene. The of turnovers, a measure of catalyst life, must be
reaction is bimolecular and the formation of greater than unity, since the catalyst would
1,2,4-trimethylbenzene has a less bulky transi- otherwise be a reagent. The total amount of
tion state than the formation of 1,3,5-trimethyl- catalyst (active sites) is typically small relative
benzene. The latter product can thus not be to the amounts of reactants and products in-
formed if the pore size and geometry is carefully volved (catalytic amounts). As a consequence,
adapted to the transition state requirements. the reactive intermediates can be treated by the
Finally, p-xylene can be selectively formed by kinetic quasi-steady-state approximation of
methylation of toluene with methanol and zeo- BODENSTEIN.
lites whose pore openings only allow p-xylene The activity of the catalyst is defined by the
to be released. The o and m isomers either number of cycles per unit time or turnovers or
accumulate in zeolite cages or are isomerized turnover frequency (TOF; unit: s1). The life of
to p-xylene. the catalyst is defined by the number of cycles
before it dies.
Figure 5. Schematic classification of the various aspects of the dynamics of surface reactions (adopted from [31])
by ERTL [31] into five categories in terms of time tions may be nonstationary transient. In certain
and length scales, as shown schematically in parameter ranges it may be oscillatory or even
Figure 5. In the macroscopic regime, the rate of chaotic. Also, there may be local variations in
a catalytic reaction is modeled by fitting empir- surface coverages which lead to coupling of the
ical equations, such as power laws, to experi- reaction with transport processes (e.g., particle
mental data, so as to describe its concentration diffusion, heat transfer). The formation of spa-
and pressure dependence and to determine rate tiotemporal concentration profiles on a meso-
constants that depend exponentially on temper- scopic scale is the consequence of these nonlin-
ature. This approach was very useful in chemi- ear dynamic phenomena.
cal engineering for reactor and process design. Since the Langmuir lattice model is not valid
Assumptions about reaction schemes (kinetic in reality, the continuum model can describe the
models) provide correlations between the sur- reaction kinetics only to a first approximation.
face coverages of intermediates and the external Interactions between adsorbed species occur,
variables, an approach that led to the Temkin and adsorbed particles occupy nonidentical
equation [78] modeling the kinetics of ammonia sites, so that complications arise in the descrip-
synthesis. tion of the reaction kinetics. Apart from the
Improved kinetic models could be developed heterogeneity of adsorption sites, surfaces may
when atomic processes on surfaces and the undergo structural transformations. Surface sci-
identification and characterization of surface ence investigations provide information on
species became available. The progress of a these effects on an atomic scale.
catalytic reaction is then described by a micro- As mentioned above, it is assumed that the
kinetics approach by modeling the macroscopic transition-state theory is valid for description of
kinetics through correlating atomic processes the rates of individual elementary steps. This
with macroscopic parameters within the frame- theory is based on the assumption that at all
work of a suitable continuum model. Continu- stages along the reaction coordinate thermal
um variables for the partial surface coverages equilibrium is established. Temperature then is
are, to a first approximation, correlated to ex- the only essential external macroscopic param-
ternal parameters (partial pressures and temper- eter. This assumption can only be valid if energy
ature) by the Langmuir lattice model of a surface exchange between all degrees of motional
consisting of identical noninteracting adsorp- freedom of the particles interacting with the
tion sites. solid acting as a heat bath is faster than the
The formulation of rate laws for the full elementary step which induces nuclear motions.
sequence of elementary reactions will usually Energy transfer processes at the quantum
lead to a set of nonlinear coupled (ordinary) level are the basic requirements for chemical
differential equations for the concentrations transformations.
(coverages) of the various surface species in- Nonlinear dynamics and the phenomena
volved. The temporal behavior of the reaction occuring at the atomic and quantum levels were
system under constant continuous-flow condi- reviewed by ERTL [31].
16 Heterogeneous Catalysis and Solid Catalysts
At steady state sd(rf rr) ¼ rfd rrd. equilibrium values. The reason for this phenom-
Hence enon is kinetic coupling between elementary
steps at the steady state, where the net rate of
sd rf ¼ rfd and sd rr ¼ rrd : ð7Þ
each step is equal to the net rate of the overall
The stoichiometric equation for the overall reaction multiplied by the stoichiometric num-
reaction can always be written such that sd is ber of the step. With kinetic coupling, a reactive
equal to unity. It is then clear that the rds is intermediate can accumulate as a reactant or be
appropriately and uniquely named as the step for depleted as a product [68,79,81].
which the forward and reverse rates are equal to The principle of microscopic reversibility is
the forward and reverse rates, respectively, of strictly valid only for reactions at equilibrium.
the overall reaction [67]. Away from equilibrium, it remains valid provided
Clearly the rds (if there is one) is the only that transition-state theory is still applicable,
kinetically significant step. A kinetically signif- which appears to be the case in heterogeneous
icant step is one whose rate constants or equi- catalysis [19]. Hence, the principle remains
librium constant appear in the rate equation for valid for any elementary step in a heteroge-
the overall reaction. In some cases there is no rds neous catalytic reaction. However, the princi-
in the Horiuti sense, but frequently only a few of ple must be applied with caution to a catalytic
the elementary steps in a catalytic cycle are cycle, as opposed to a single elementary reac-
kinetically significant. It is sometimes said that tion. If valid, the principle of microscopic
a rate-limiting step is the one having the smallest reversibility allows the calculation of a rate
rate constant. However, rate constants can often constant if the second rate constant and
not be compared because they have different the equilibrium constant Ki of an elementary
dimensions. reaction i are known: kfi/kri ¼ Ki.
The relative importance of rate constants of
elementary steps in a catalytic cycle provides
useful guidelines for the development of activity 2.2.2. Application of Microkinetic
and selectivity. This can be achieved by Analysis
parametric sensitivity analysis [84], which was
first proposed by CAMPBELL [85] for analysis of Two of the most intensively studied systems in
kinetic parameters of catalytic reactions (see heterogeneous catalysis are CO oxidation over
also ref. [74]). CAMPBELL [85] defined a degree noble metals and ammonia synthesis. In both
of rate control for any rate constant ki in a cases, pioneering work using microkinetic anal-
catalytic cycle turning over at a rate r ysis led to a better understanding of the catalytic
Xi ¼ ki =r@r=@ki ð8Þ cycle and new fundamental insights, which
supported design and optimization of the cata-
where the equilibrium constant for step i and all lytic applications. In industry, CO oxidation
other rate constants are held constant. The main over Pt and Pd was one of the first systems used
advantage of this mathematical operation is its for automobile emission control and is a key
simplicity. It turns out that HORIUTI’s rds, as the intermediate step in many technical systems for
only kinetically significant step in a catalytic hydrocarbon transformations. Ammonia syn-
cycle, has a degree of rate control Xi ¼ 1, thesis — once the driving force for a new
whereas the X values for all other steps are chemical industry — still is one of the most
equal to zero. Clearly, all intermediate values important technical applications of heteroge-
of Xi are possible, and probable in most cases. neous catalysis. These technical aspects of CO
As a catalytic cycle turns over at the quasi- oxidation and ammonia synthesis are discussed
steady state, the steady-state concentrations in Chapter Industrial Application and Mechan-
(coverages) of the reactive intermediates may isms of Selected Technically Relevant Reac-
be significantly different from the values that tions. Since CO oxidation on noble metals has
they would attain if they were at equilibrium been the major working system in surface
with fluid reactants or products. The steady- science and has led to elucidation of many
state concentrations (coverages) of reactive in- fundamental issues of reactions on catalytic
termediates may be lower or higher than the surfaces, such as oscillatory kinetics and
18 Heterogeneous Catalysis and Solid Catalysts
spatio-temporal pattern formation [86], this sys- acterizing the elementary steps on the Pd(111)
tem will be exemplarily used for the illustration surface (Fig. 6). Most of the energy is liberated
of microkinetic analysis. upon adsorption of the reactants, and the activa-
CO oxidation on noble metals (Pt, Pd, etc.) tion barrier for the combination of the adsorbed
intermediates is relatively small; this step is only
COþ1/2O2 !CO2 ð9Þ weakly exothermic, and the heat of adsorption
is relatively well understood, based on surface (activation energy for desorption) of CO2 is very
science studies. Molecular oxygen is chemi- low.
sorbed dissociatively, while CO binds asso- The sequence of elementary steps (10) –
ciatively [87,88]. Molecular CO then reacts with (12) is quite simple. The overall kinetics, how-
atomic oxygen in the adsorbed state: ever, is not. This is due to the nonuniformity of
the surface and segregation of the reactants into
O2 þ2* !O2;ads !2Oads ð10Þ surface domains at higher coverages. As a con-
sequence, the reaction between the surface spe-
COþ*!COads ð11Þ cies COads and Oads can only occur at the
boundaries between these domains. A simple
Langmuir – Hinshelwood treatment of the ki-
COads þOads !CO2 þ2* ð12Þ netics is therefore ruled out, except for the
special case of low surface coverages by COads
Here * denotes a free surface site and the
and Oads, when these are randomly distributed
subscript “ads” an adsorbed species. The reac-
and can be considered to a first approximation as
tion steps (10)–(12) suggest that CO oxidation is
being part of an ideal surface.
a Langmuir – Hinshelwood process in which
both reacting species are adsorbed on the cata-
lyst surface. The reverse of reaction (10), i.e., 2.2.3. Langmuir – Hinshelwood –
the recombination of two oxygen atoms is ki- Hougen – Watson Kinetics [89,70,72,90]
netically insignificant at temperatures below
ca. 600 K. Possible Eley – Rideal steps such The Langmuir – Hinshelwood – Hougen –
as (13), in which a gas-phase molecule reacts Watson (LHHW) approach is based on the
with an adsorbed species Langmuir model describing the surface of a
COþOads !CO2 þ* ð13Þ catalyst as an array of equivalent sites which
do not interact either before or after chemisorp-
were found to be unlikely. tion. Further, for derivation of rate equations, it
Quantitative experiments led to a schematic is assumed that both reactants and products are
one-dimensional potential-energy diagram char- equilibrated with surface species that react on
Figure 6. Schematic one-dimensional potential-energy diagram characterizing the CO þ O2 reaction on Pd(111) [88]
Heterogeneous Catalysis and Solid Catalysts 19
the surface in a rate-determining step. Surface As an example for a typical LHHW rate
coverages are correlated with partial pressures equation consider the reaction
or concentrations in the fluid phase by means of
Langmuir adsorption isotherms. It was men- AþB Ð C:
tioned above that the Langmuir model is unre-
alistic. Moreover, it was demonstrated in Sec- The form of rate equation is as follows [91]:
tion Concepts of Reaction Kinetics (Microki- krds NT Ki ðPA PB PC =Keq Þ
netics) that the surface coverages of adsorbed r¼ P
species are by no means identical to the equi- ð1þKA PA þKB PB þKC PC þ j Kj Pj Þn
librium values predicted by the Langmuir ad- rate factor driving force
sorption isotherm for reaction systems in which ¼
inhibition term
kinetic coupling occurs, and rate-determining ð14Þ
steps do not generally exist.
Despite these weaknesses, the LHHW kinet- The numerator is a product of the rate con-
ics approach has proved valuable for modeling stant of the rds krds, the concentration of active
heterogeneous catalytic reactions for reactor and sites NT, adsorption equilibrium constants Ki,
process design. The kinetic parameters which and the driving force for the reaction. The latter
are determined by fitting the rate equations to is a measure of how far the overall reaction is
experimental data, however, do not have a from thermodynamic equilibrium. The overall
straightforward physical meaning. As an alter- equilibrium constant Keq, can be calculated from
native, simple power-law kinetics for straight- thermodynamics. The denominator is an inhibi-
forward reactions (e.g., A ! B) can be used for tion term which takes into account the competi-
technical application. tive adsorption of reactants and products.
Often it is difficult to discriminate between two A few examples of LHHW rate equations are
or more kinetic models within the accuracy limits summarized in Table 3. A collection of useful
of the experimental data. Sophisticated mathe- LHHW rate equations and kinetic data for
matical procedures have therefore been developed almost 100 industrially important catalytic re-
for the discrimination of rival models [91]. actions is available in [92].
2.2.4. Activity and Selectivity when one reactant transforms into several pro-
ducts in parallel (type II):
Catalytic activity is expressed in terms of
reaction rates, preferably normalized to the
surface area of the active phase (e.g., metal
surface area for supported metal catalysts).
These surface areas can be obtained by suitable
chemisorption techniques (see Section Physi-
cal Properties). As an alternative to these areal or in consecutive reactions (type III):
rates, specific rates are also used which are
normalized to catalyst weight. The best possi-
ble measure of catalytic activity, however, is
the turnover rate or turnover frequency, since it
is normalized to the number of active sites and The selectivity is defined as the ratio of the
represents the rate at which the catalytic cycle rate of formation of the desired product to the
turns over. For comparison of rates reported by rate of consumption of the starting material [93].
different research groups, the methodology for Thus, the selectivities for product X for the first-
the determination of the number of active sites order reactions I and II is r1/(r1 þ r2), whereas it
must be carefully reported. The hitherto unre- is (r1 r2)/r1 for type III.
solved problem is that the site densities mea- In the case of type I or II reactions, selectivity
sured prior to the catalytic reaction are not for X or Y is independent of the conversion of
necessarily identical to those available under the starting material. In type III reactions, the
reaction conditions. selectivity for X is 100 % initially, decreases
A readily available measure of catalytic ac- gradually with increasing conversion, and drops
tivity is space – time yield, expressed in units of to zero at 100 % conversion. At an intermediate
amount of product made in the reactor per unit conversion, there is a maximum yield of X
time and unit reactor volume. which depends on the ratio of the rate constants
A considerable obstacle for the comparison k1 and k2 of the rates r1 and r2. The integrated
of catalytic activities for a given reaction that rate equations are:
were obtained in different laboratories for the ½A ¼ expðk1 tÞ ð15Þ
same catalyst is the use of different reactors. For
a series of catalysts, reasonable comparisons of
activities or rates are possible when relative ½X ¼ k1 =ðk2 k1 Þ ½expðk1 tÞexpðk2 tÞ
values are used. ð16Þ
Conversion data alone, or conversion versus
time plots are not sufficient as a measure of where [A] is the concentration of unconverted
catalytic activity. A, [X] the concentration of A converted to
Selectivity can be defined as the amount of product X, and t time. The maximum yield is
desired product obtained per amount of con- reached at
sumed reactant. Selectivity values are only use- t ¼ ðk1 k2 Þ1 lnðk1 =k2 Þ ð17Þ
ful if the conversion is also reported. A simple
measure of selectivity is the yield (yield ¼ se-
lectivity conversion). Selectivities can also
be used to indicate the relative rates of two or 2.3. Molecular Modeling in
more competing reactions; competition may Heterogeneous Catalysis
occur when several reactants form products in
parallel (type I): Modeling of catalytic reactions is applied at
many levels of complexity covering several
orders of length and time scales. It ranges from
complete description of the dynamics of a
reaction through adsorbate – adsorbate interac-
tions to the simple mean-field approximations
Heterogeneous Catalysis and Solid Catalysts 21
Ab initio calculation Most fundamental approach Not yet significant in heterogeneous catalysis
Density functional theory (DFT) Replacement of the N-electron wave Dynamics of reactions, activation barriers, adsorbed
function by the electron density structures, frequencies
Kinetic Monte Carlo (kMC) Details of dynamics neglected Adsorbate – adsorbate interactions on catalytic surfaces
and nanoparticles
Langmuir – Hinshelwood Detailed configuration of the adsorbate Microkinetic modeling of catalytic reactions in technical
(mean-field approximation, MF) structure neglected systems
Power-law kinetics All mechanistic aspects neglected Scaleup and reactor design for “black-box” systems
and macrokinetic models discussed in Section costs are relatively low. Disadvantages are the
Langmuir – Hinshelwood – Hougen – Watson limited number of atoms in the cluster, currently
Kinetics. The different approaches can be rep- (ca. 2008) a few hundred, and the fact that metal
resented in a hierarchy of models (Table 4). clusters in general have different properties to
In this section, frequently used models are three-dimensional metals. Some prominent soft-
presented that either describe the molecular be- ware tools using the cluster algorithm are
havior of the catalytic cycle directly or are based GAUSSIAN [94] and TURBOMOLE [95].
on the molecular picture. Often, the output of a The second approach, usually denoted by the
computation using a more sophisticated method terms “planar waves” or “periodic boundaries”,
serves as input for a computation using a less is much more popular in heterogeneous cataly-
detailed model; for instance activation energies sis. The algorithm is based on a supercell ap-
computed by DFTare often used as parameters in proach, i.e., structures to be calculated must be
kinetic Monte Carlo and simulations. periodic in three dimensions. This approach is
especially advantageous when considering sur-
face structures, because a real solid surface is
2.3.1. Density Functional Theory built on expansion from a small metal cluster or
metal slab into three dimensions. In particular,
In real ab initio calculations, in which the time- the metallic properties are better described. The
dependent Schr€ odinger equation is solved to “third dimension” is a disadvantage, because the
obtain the complex N-electron wavefunction solid cell must be periodic in this direction as
Y, the number of atoms of the system studied well. Aside from the problem of choosing ap-
is very limited, and therefore quantum mechan- propriate functionals, the size of the cell and the
ical calculations in heterogeneous catalysis are convergence criteria are significant for DFT
almost exclusively based on the DFT approach. computations to provide reliable information.
Based on the Hohenberg – Kohn theorem, the Some prominent software tools using the planar
ground-state energy of an atom or molecule is waves approach are CASTEP [96], DACAPO
completely determined by the electron density. [97], and VASP [98].
Even though the exact functional dependence of the Even though still very computer time con-
energy on the electron density is not known, ap- suming, DFT can be used to calculate the stabil-
proximate functionals can be developed (Kohn – ity and frequencies for all reactants, intermedi-
Sham formalism) that lead to the much simpler ates, and products, as well as activation barriers
computed electron density. of the elementary reactions [99–105]. Recently,
There are two major methods for DFT simu- complete reaction mechanisms including prop-
lations of catalytic systems: In the first, the erties of intermediates have been developed
cluster algorithm, the molecules studied are based on DFT computations alone, for instance,
metal clusters including the adsorbed particles. for CO oxidation over RuO2(110) [105], epoxi-
The advantage of this approach is that the special dation of ethylene over Ag [106], methanol
shape of catalytic clusters can be taken into decomposition over Cu [107], ammonia synthe-
account, and methods developed for gas-phase sis over Ru [108], and decomposition of N2O on
chemistry can be used, so that computational Fe-ZSM-5 [109]. DFT simulation not only helps
22 Heterogeneous Catalysis and Solid Catalysts
to understand the fine details of catalytic reac- of the adsorbate – adsorbate interactions, such
tions, for instance, the effect of surface steps on as the formation of ordered structures, may
stability of intermediates [108] and the impact of appear at low temperature and pressure, where
coverage on activation energies [110], but also to diffusion is slow and the rate of impingement of
elucidate the broader picture, for example, by gas-phase molecules is small, respectively. Un-
finding a relationship between activation energy der these conditions kMC may be the only
and chemisorption energy [111]. description that is accurate, while at high tem-
perature and pressure, the adsorbates are rather
randomly dispersed on the surface, and the
2.3.2. Kinetic Monte Carlo Simulation assumptions of the mean-field approximation
may be valid.
Diffusion of adsorbates on catalytic surfaces is
crucial for catalytic reactions. Furthermore, in-
teractions between adsorbates can be substantial 2.3.3. Mean-Field Approximation
and lead to ordered structures such as islands [119–122]
and influence the energetic state of the surface,
which also implies dependence of the activation In the mean-field approximation, a continuous
barriers for adsorption, diffusion, reaction, and description is considered instead of the detailed
desorption on the surface coverage and the configurations of the system discussed above.
actual configuration of the adsorbates. The ad- Hence, the local state of the catalytic surface on
sorbed species can be associated with a surface the macroscopic or mesoscopic scale can be
site, and thus a lattice representation of a two- represented by mean values by assuming ran-
dimensional surface can be constructed. In the domly distributed adsorbates on the surface,
case of catalytic particles, a three-dimensional which is viewed as being uniform. The state of
structure can be used with individual two-di- the catalytic surface is described by the temper-
mensional facets that can differ in their catalytic ature T and a set of surface coverages ui, that is,
activity. In the three-dimensional case, special the fraction of the surface covered with adsor-
care is needed for appropriate treatment of bate i. The surface temperature and the cov-
edges and corners. Even reconstruction of sur- erages depend on time and spatial position in the
faces can be taken into account. At each surface macroscopic system (reactor), but are averaged
site the local environment (presence of adsor- over microscopic local fluctuations. Under
bates, catalyst morphology/crystal phase) will those assumptions a chemical reaction can be
determine the activation energies. If the inter- defined as
actions between the adsorbates, the surface, and
the gas phase are known, such parameters could Ng þN
X s þNb Ng þN
X s þNb
0 00
theoretically be derived from DFT simulations, nik Ai ! nik Ai
and the kinetics can be computed by the kinetic i¼1 i¼1
Monte Carlo method (kMC) [105,112–118].
Each molecular event, i.e., adsorption, desorp- where Ai denote gas-phase species, surface spe-
tion, reaction, diffusion, is computed and leads cies, and bulk species. The Ns surface species
to a new configuration of adsorbed species on are those that are adsorbed on the top monoa-
the surface lattice. Aside from this very detailed tomic layer of the catalytic particle, while the Nb
description of the process, time averaging of the bulk species are those found in the inner solid
time-dependent computed reaction rates and catalyst.
surface coverage can then lead to overall rate Steric effects of adsorbed species and various
expressions. However, the computational effort configurations, e.g., type of chemical bond be-
needed is immense, not only due to the kMC tween adsorbate and solid, can be taken into
simulation but also because of the huge number account by using the following concept: The
of fundamental DFT computations needed to surface structure is associated with a surface site
provide reliable activation barriers for all possi- density G that describes the maximum number
ble individual steps. Experimental derivation of of species that can be adsorbed on unit surface
this information is even more exhausting. Most area. Each surface species is associated with a
Heterogeneous Catalysis and Solid Catalysts 23
coordination number si describing the number reaction mechanism can be proposed based on
of surface sites which are covered by this spe- experimental surface-science studies, on analo-
cies. Under the assumptions made, a multistep gy to gas-phase kinetics and organometallic
(quasi-elementary) reaction mechanism can be compounds, and on theoretical studies, in-
set up. The molar net production rate is then cluding DFT and kMC calculations as well as
given as semi-empirical calculations [123,124]. This
Ng þN s þNb
mechanism should include all possible paths
X
Ks Y n
0
for formation of the chemical species under
si ¼ nik kf k cj jk :
k¼1 j¼1
consideration in order to be “elementary-like”
and thus applicable over a wide range of con-
where Ks is the number of surface reactions, ci ditions. The mechanistic idea then needs to be
are the species concentrations, which are given, evaluated against numerous experimentally de-
e.g., in mol m2 for the Ns adsorbed species and rived data, which are compared with theoretical
in, e.g., mol m3 for the Ng and Nb gaseous and predictions based on the mechanism. Here,
bulk species. With Qi ¼ ci si G1 , the variations simulations of the laboratory reactors require
of surface coverages follow: appropriate models for all significant processes
@Qi si si in order to evaluate the intrinsic kinetics. Sen-
¼ : sitivity analysis leads to the crucial steps in the
@t G mechanism, for which refined kinetic experi-
Since the temperature and concentrations of ments and data may be needed.
gaseous species depend on the local position in Since the early 1990s, many groups have
the reactor, the set of surface coverages also developed surface reaction mechanisms follow-
varies with position. However, no lateral inter- ing these concepts. In particular, oxidation re-
action of the surface species between different actions over noble metals have been modeled
locations on the catalytic surface is modeled in extensively, such as those of hydrogen [125–
this approach. This assumption is justified by 129], CO [130–132], methane [133–137], and
the fact that the computational cells in reactor ethane [138–140] over Pt and formation of
simulations are usually much larger than the synthesis gas over Rh [141–142]. More recently,
range of lateral interactions of the surface pro- mechanisms have been established for more
cesses. In each of these cells, the state of the complex systems such as three-way cata-
surface is characterized by mean values (mean- lysts [143] and chemical vapor deposition
field approximation). (CVD) of diamond [144,145], silica [146], and
The binding states of adsorption of all species nanotubes [147]. A more detailed survey on
vary with the surface coverage, as discussed in existing microkinetic models can be found
Section Kinetic Monte Carlo Simulation. This in [121].
additional coverage dependence can be mod-
eled in the expression for the rate coefficient by
an additional function leading to: 3. Development of Solid Catalysts
Ns
Eak Y mik e i k Qi The development of a catalytic process involves
kf k ¼ Ak T exp
bk
Q exp :
RT i¼1 i RT the search for the catalyst and the appropriate
reactor, and typically occurs in a sequence of
For adsorption reactions sticking coefficients steps at different levels. Figure 7 shows a
are commonly used, which can be converted to scheme summarizing this evolutionary process.
conventional rate coefficients. Small-scale reactors are used for screening to
determine the optimal catalyst formulation.
Since catalyst development and sequential
2.3.4. Development of Multistep Surface screening are slow and cost-intensive processes,
Reaction Mechanisms [122] high-throughput experimentation (HTE) tech-
niques [149–155] which permit parallel testing
The development of a reliable surface reaction of small amounts of catalyst in automated sys-
mechanism is a complex process. A tentative tems have attracted great interest (see also !
24 Heterogeneous Catalysis and Solid Catalysts
Figure 7. Scheme for catalyst development and design (from [148], modified)
Figure 8. Calculated turnover frequencies (TOF) for ammonia synthesis as a function of the adsorption energy of nitrogen for
various transition metals and alloys (reprinted with permission from [162]).
N2, an optimum strength of the metal – nitrogen catalysts; (3) confined catalysts (ship-in-a-bot-
interaction is required for high ammonia syn- tle catalysts); (4) hybrid catalysts; (5) polymer-
thesis activity. The resulting volcano-shaped ization catalysts, and several others. The select-
relationship shows, in agreement with experi- ed examples not only include materials which
mental evidence, that Ru and Os, followed by are in use in industry, but also materials which
Fe, are the best pure metal catalysts (Figure 8). are not yet mature for technological application
First-principles DFTcalculationswere used to but which have promising potential.
predict that alloys of metals with high and low
adsorption energy should give rise to binding
energies close to the optimum. Based on these 4.1. Unsupported (Bulk) Catalysts
calculations, a Co – Mo catalyst was developed
that has much higher ammonium synthesis activ- 4.1.1. Metal Oxides
ity than the individual metals and is even better
than Ru and Fe at low ammonia concentrations. Oxides are compounds of oxygen in which the O
atom is the more strongly electronegative com-
ponent. Oxides of metals are usually solids.
4. Classification of Solid Catalysts Their bulk properties largely depend on the
bonding character between metal and oxygen.
Solid catalysts are extremely important in large- Metal oxides have widely varying electronic
scale processes [163–167] for the conversion of properties and include insulators (e.g., Al2O3,
chemicals, fuels, and pollutants. Many solid SiO2), semiconductors (e.g., TiO2, NiO, ZnO),
materials (elements and compounds) including metallic conductors (typically reduced transi-
metals, metal oxides, and metal sulfides, are tion metal oxides such as TiO, NbO, and tung-
catalysts. Only a few catalytic materials used in sten bronzes), superconductors (e.g., BaPb1x-
industry are simple in composition, e.g., pure BixO3), and high-Tc superconductors (e.g.,
metals (e.g., Ni) or binary oxides (such as g- YBa2Cu3O7x).
Al2O3, TiO2). Typical industrial catalysts, how- Metal oxides make up a large and important
ever, consist of several components and phases. class of catalytically active materials, their sur-
This complexity often makes it difficult to face properties and chemistry being determined
assess the catalytic material’s structure. by their composition and structure, the bonding
In the following a variety of families of character, and the coordination of surface atoms
existing catalysts are described, and selected and hydroxyl groups in exposed terminating
examples are given. These families include crystallographic faces. They can develop acid-
(1) unsupported (bulk) catalysts; (2) supported base and redox properties. Metal oxides can
26 Heterogeneous Catalysis and Solid Catalysts
have simple composition, like binary oxides, but these oxides can be described as close-packed
many technologically important oxide catalysts layers of oxo anions with Al3þ cations distrib-
are complex multicomponent materials. uted between tetrahedral and octahedral vacan-
cy positions. Stacking variations of the oxo
4.1.1.1. Simple Binary Oxides anions result in the different crystallographic
Simple binary oxides of base metals may behave forms of alumina. The most commonly used
as solid acids or bases or amphoteric materi- transitional phases are h- and g-Al2O3, which
als [168]. These properties are closely related to are often described as defect spinel struc-
their dissolution behavior in contact with aque- tures [171] that incorporate Al3þ cations in
ous solutions. Amphoteric oxides (e.g., Al2O3, both tetrahedral and octahedral sites. The Al
ZnO) form cations in acidic and anions in basic sublattice is highly disordered, and irregular
milieu. Acidic oxides (e.g., SiO2) dissolve with occupation of the tetrahedral interstices results
formation of acids or anions. Transition metal in a tetragonal distortion of the spinel structure.
oxides in their highest oxidation state (e.g., There is a higher occupancy of tetrahedral cat-
V2O5, CrO3) behave analogously. Basic oxides ion positions in g-Al2O3, and a higher density of
(e.g., MgO, lanthanide oxides) form hydroxides stacking faults in the oxygen sublattice of h-
or dissolve by forming bases or cations. These Al2O3. Crystallites are preferentially terminated
dissolution properties must be considered when by anion layers, and these layers are occupied by
such oxides are used as supports and impreg- hydroxyl groups for energetic reasons [172].
nated from aqueous solutions of the active phase Acidic and basic sites and acid-base pair sites
precursor [169,170]. The dissolution properties have been identified on the surfaces of alumi-
also are closely related to the surface properties nas [174]. Thermal treatment of hydroxylated
of the oxides in contact with a gas phase, where oxides leads to partial dehydroxylation with
the degree of hydration/hydroxylation of the formation of coordinatively unsaturated O2
surface is a critical parameter. Silica, alumina ions (basic sites) and an adjacent anion vacancy
and magnesia are commonly used catalysts and which exposes 3- or 5-coordinate Al3þ cations
catalyst supports representative for a wide range (Lewis acid sites). The remaining hydroxyl
of surface acid – base properties. groups can be terminal or doubly or triply
bridging with the participation of Al3þ in tetra-
Aluminas are amphoteric oxides, which hedral and/or octahedral positions. The proper-
form a variety of different phases depending on ties of the resulting OH species range from
the nature of the hydroxide or oxide hydroxide very weakly Brønsted acidic to rather strongly
precursor and the conditions of their thermal basic and nucleophilic [172,174]. As a result
decomposition. Bayerite, nordstrandite, boehm- of this complexity, alumina surfaces develop a
ite, and gibbsite can be used as starting materi- rich surface chemistry and specific catalytic
als. The thermal evolution of the various poorly properties [175].
crystalline transitional phases (namely h-, Q-, Besides their intrinsic catalytic properties
g-, x-, and k-Al2O3) and of the final crystalline, and their use as catalysts in their own right
thermodynamically stable a-Al2O3 phase (co- (e.g., for elimination reactions, alkene isomeri-
rundum) is shown in Figure 9. The structures of zation [175], and the Claus process [176]),
Figure 9. The dehydration sequences of the aluminum trihydroxides in air (adopted from [173])
Heterogeneous Catalysis and Solid Catalysts 27
aluminas are frequently used as catalyst sup- material has MFI structure and can be consid-
ports for oxides and metals. The surface area and ered as the parent siliceous extreme of zeolite
particle size of aluminas can be controlled by the ZSM-5.
preparation conditions, and their redox and Large-pore mesoporous structures, the so-
thermal stability give the supported active called porosils, have also been reported [180–
phases high stability and ensure a long catalyst 182]. The dimensions of their linear and paral-
lifetime. lel pores can be varied from 2 to 10 nm in a
regular fashion. These pores can therefore
Silicas are weakly Brønsted acidic oxides accommodate bulky molecules and functional
which occur in a variety of structures such as groups.
quartz, tridymite and cristobalite (! Sili- The incorporation of foreign elements such
ca) [177,178]. The most commonly used silica as Al3þ substituting for Si4þ induces Brønsted
in catalysis is amorphous silica. The building acidity and creates activity for acid catalysis.
blocks of silica are linked SiO4 tetrahedra, with
each O atom bridging two Si atoms. Bonding Magnesium oxide is a basic solid. It has
within the solid is covalent. At the fully hydrated the simple rock salt structure, with octahedral
surface, the bulk structure is terminated by coordination of magnesium and oxygen. Ab
hydroxyl (silanol) groups, SiOH [174,177,178]. initio molecular orbital calculations indicated
Two types of these groups are usually distin- that the electronic structure is highly ionic, with
guished: isolated groups and hydrogen-bonded the Mg2þO2 formalism being an accurate re-
vicinal groups. Fully hydrated samples, cal- presentation of both bulk and surface struc-
cined at temperatures below 473 K, may con- tures [183]. The lattice is commonly envisaged
tain geminal groups Si(OH)2 [174,177,178]. to terminate in (100) planes incorporating five-
Heating in vacuum removes the vicinal groups coordinate (5c) Mg2þ and O2 ions [184] (see
by dehydroxylation, i.e., condensation to form Figure 10). This model appears to be physically
H2O and Si – O – Si linkages (siloxane bridges). accurate for MgO smoke, which may be re-
Complete removal of the hydroxyl groups occurs garded as a model crystalline metal oxide
at temperatures well above 973 K in vacuo and is support [185]. Although the (100) plane is
believed to result in significant changes in surface electrically neutral, hydroxyl groups are present
morphology. on the surfaces of polycrystalline MgO. These
The surface hydroxyl groups are only weakly groups and the O2- anions are responsible for the
Brønsted acidic and therefore hardly develop any basic properties, coordinatively unsaturated
catalytic activity. They are, however, amenable Mg2þ ions being only weak Lewis acid sites.
to hydrogen-bonding [179] and they are usually The hydroxyl groups are also highly
regarded as the most reactive native surface nucleophilic.
species, which are available for functionalization These properties dominate the surface chem-
of silicas. The siloxane bridges are (at least after istry of MgO. Organic Brønsted acids have been
heating at elevated temperatures) essentially un- shown to be chemisorbed dissociatively to form
reactive. For this reason and because of the low surface-bound carbanions and surface hydroxyl
acidity of silanol groups, silicas are not used as groups [186]. Even the heterolytic dissociative
active catalysts, but they play an important role as adsorption of dihydrogen on polycrystalline
oxide supports and for the synthesis of functio- MgO has been reported. Mg2þO2 pairs with
nalized oxide supports (see Section Supported Mg2þ and O2 in 4- or 3-coordination seem to
Sulfide Catalysts). play a crucial role.
Tailored silicas can be synthesized by con- The presence of low-coordinate Mg2þ and
2
trolling the preparation conditions [177,178]. O ions (see Figure 10) on the MgO surface
Thus, surface area, particle size and morphology, after activation at high temperatures has been
porosity and mechanical stability can be varied demonstrated [184,187,188], and the unique
by modification of the synthesis parameters. reactivity of 3c centers has been discussed
In addition to amorphous silicas, the crystal- [189].
line microporous silica silicalite I can be ob- MgO has also been used as a host matrix for
tained by hydrothermal synthesis [180]. This transition metal ions (solid solutions) [190].
28 Heterogeneous Catalysis and Solid Catalysts
Figure 10. Representation of a surface plane (100) of MgO showing surface imperfections such as steps, kinks, and corners
wich provide sites for ions of low coordination (adopted from [184]).
These materials permit the properties of isolated VOx/TiO2, which plays a significant role in
transition metal ions to be studied. selective oxidation and NOx reduction catalysis.
Titania is a semiconductor with a wide band
Transition metal oxides [191–193] can be gap and as such is an important material for
structurally described as more or less dense photocatalysis [194,195].
packings of oxide anions, the interstices of Zirconia has attracted significant interest in
which are occupied by cations. The bonding, the recent past as a catalyst support and as a base
however, is never purely ionic, but rather mixed material for the preparation of strong solid acids
ionic-covalent, sometimes also developing me- by surface modification with sulfate or tungstate
tallic character (e.g., bronzes). The surface of groups [196]. The most important crystallo-
these oxides is often partially occupied by hy- graphic phases of ZrO2 for catalytic applica-
droxyl groups, so they possess some acidic tions are tetragonal and monoclinic. The latter is
character. However, it is the variability in oxi- the thermodynamically stable phase. Higher
dation states and the possibility of forming surface areas, however, are developed by the
mixed-valence and nonstoichiometric com- metastable tetragonal phase, which is stabilized
pounds that are responsible for their important at low temperatures by sulfate impurities or
redox catalytic properties. The most frequently intentional addition of sulfate or tungstate.
used transition metal oxides are those of the ZrO2 is the base material for the solid-state
early transition metals (mostly suboxides). electrolyte sensor for the measurement of oxy-
Fields of application are particularly selective gen partial pressure in, e.g., car exhaust gas-
oxidation and dehydrogenation reactions. es [197]. The solid electrolyte shows high bulk
Titania TiO2 exists in two major crystallo- conductivity for O2 ions.
graphic forms: anatase and rutile. Anatase is the Other transition metal oxides are used as
more frequently used modification since it de- supported catalysts or as constituents of com-
velops a larger surface area, although it is a plex multicomponent catalysts.
metastable phase and may undergo slow trans- Only a few examples are reported on the
formation into the thermodynamically stable application of the unsupported binary oxides as
rutile phase above ca. 900 K. Vanadium impu- catalysts. Iron oxide Fe2O3 and chromium
rities seem to accelerate the rutilization above oxide Cr2O3 catalyze the oxidative dehydroge-
820 K. Other impurities such as surface sulfate nation of butenes to butadiene. Fe2O3-based
and phosphate seem to stabilize the anatase catalysts are used in the high-temperature wa-
phase. The anatase ! rutile phase transition ter gas shift reaction [198] and in the dehydro-
must be sensitively controlled for supported genation of ethylbenzene [199]. Vanadium
Heterogeneous Catalysis and Solid Catalysts 29
pentoxide V2O5 is active for the selective oxi- n-membered rings. Small-pore zeolites contain 6-
dation of alkenes to saturated aldehydes [200]. or 8-membered rings (diameter d: 2.8 < d < 4
Acidic transition metal oxides such as vanadi- A), medium-pore zeolites
contain 10-membered
um pentoxide and molybdenum trioxide MoO3 rings (5 < d < 6 A) and the openings of large-
can be used for the synthesis of formaldehyde pore zeolites are constructed of 12-membered
by oxidative dehydrogenation of methanol, rings (d > 7 A). Examples of small-pore zeolites
while the more basic iron oxide Fe2O3 leads are sodalite and zeolite A, of medium-pore zeo-
to total oxidation [201]. Zinc oxide ZnO is used lites ZSM-type zeolites (see Figure 11), while
as a catalyst for the oxidation of cyclohexanol large-pore zeolites include faujasites and zeolites
to cyclohexanone. X and Y (see Figure 11).
The H forms of zeolites develop strong
4.1.1.2. Complex Multicomponent Oxides Brønsted acidity and play a major role in
Complex multicomponent oxides play a major large-scale industrial processes such as catalytic
role as catalytic materials. cracking, the Mobil MTG (methanol-to-gaso-
line) process and several others.
Aluminum silicates are among the most Besides Si and Al as Tatoms P atoms can also
important ternary oxides. Four-valent Si atoms be incorporated in zeolite structures. In addi-
are isomorphously substituted by trivalent Al tion, transition metal atoms such as Ti, V, and Cr
atoms in these materials. This substitution cre- can substitute for Si, which leads to oxidation
ates a negatively charged framework of inter- catalysts of which titanium-silicalite-1 (TS1) is
connected tetrahedra. Exchangeable cations are the most outstanding catalyst for oxidation,
required for charge compensation when protons hydroxylation, and ammoxidation with aqueous
are incorporated as charge-compensating ca- H2O2 [205].
tions, OH groups bridging Si and Al atoms are Basic properties can be created in zeolites
created which act as Brønsted acidic sites. by ion-exchange with large alkali metal ions
such as Csþ and additional loading with
Amorphous silica – alumina can be pre- CsO [206].
pared by precipitation from solution. This
mixed oxide is a constituent of hydrocarbon Aluminum phosphates (AlPO) [207,208]
cracking catalysts. are another family of materials whose structures
are similar to those of zeolites. They can be
Zeolites Hydrothermal synthesis can be regarded as zeolites in which the T atoms are Si
used for preparation of a large family of crystal- and Al. More recently they have been named
line aluminosilicates, known as zeolites (! zeotypes, the T atoms of which are Al and P. In
Zeolites), which are microporous solids with pore contrast to aluminosilicate zeolites, AlPOs typ-
sizes ranging from ca. 3 to 7 A [180,202,203]. ically have a Al/P atomic ratio of 1/1, so that the
Characteristic properties of these structurally framework composition [AlPO4] is neutral.
well-defined solids are selective sorption of small Therefore, these solids are nonacidic and have
molecules (molecular sieves), ion exchange, and hardly any application as catalysts. However,
large surface areas. Zeolites possess a framework acidity can be introduced by substituting Al3þ
structure of corner-linked SiO4 4 and AlO4 5 by divalent atoms, which yields metal alumino-
tetrahedra with two-coordinate oxygen atoms that phosphates (MAPOs), e.g., MnAPO or CoAPO,
bridge two tetrahedral centers (so-called T or by partial substitution of formally pentavalent
atoms). Zeolite frameworks are open and contain P by Si4þ to give silicoaluminophosphates
channels (straight or sinusoidal) or cages of (SAPO). The AlPO family contains members
spherical or other shapes. These cages are typi- with many different topologies which span a
cally interconnected by channels. The evolution wider range of pore diameters than aluminosili-
of several zeolite structures from the primary cate zeolites.
tetrahedra via secondary building blocks is dem- Mesoporous solid acids with well-defined
onstrated in Figure 11 [204]. The diameter of the pore structures can be obtained by replacing a
channels is determined by the number n of T certain amount of Si atoms in MCM-type oxides
atoms surrounding the opening of the channels as by Al atoms.
30 Heterogeneous Catalysis and Solid Catalysts
Figure 11. Structures of four representative zeolites and their micropore systems and dimensions [204]
Clays (! Clays) are aluminosilicate Mixed metal oxides are multimetal multi-
minerals (montmorillonite, phyllosilicates phase oxides which typically contain one or
(smectites), bentonites, and others). Montmo- more transition metal oxide and exhibit signifi-
rillonite is an aluminohydroxysilicate and is the cant chemical and structural complexi-
main constituent of most clay minerals. It is a ty [210,211]. Their detailed characterization is
2 : 1 clay, i.e., one octahedral AlO6 layer is therefore extremely difficult, and structure-
sandwiched between two tetrahedral SiO4 property relationships can only be established
layers. Montmorillonites are reversibly swella- in exceptional cases. Bulk mixed metal oxide
ble and possess ion-exchange capacity. They catalysts are widely applied in selective oxida-
can be used as catalyst supports. The structural tion, oxydehydrogenation, ammoxidation and
layers can be linked together by introducing other redox reactions. Several examples of
inorganic pillars which prevent the layers from mixed metal oxides and their application in
collapsing at higher temperatures when the industrial processes are summarized in Table 5.
swelling agent is evaporated (pillared
clays) [209]. A bimodal micro-/mesoporous Vanadium phosphates (e.g., VOHPO4
pore size distribution can thus be obtained. 0.5 H2O) are precursors for the so-called VPO
Pillaring can be achieved with a wide variety catalysts, which catalyze ammoxidation reac-
of reagents including hydroxy aluminum poly- tions and the selective oxidation of n-butane to
mers, zirconia hydroxy polymers, silica, and maleic anhydride. It is proposed that the crys-
silicate pillars. Catalytically active components talline vanadyl pyrophosphate phase (VO)2P2O7
may be built in by the pillaring material, e.g., is responsible for the catalytic properties of the
transition metal oxide pillars. VPO system. The vanadium phosphate precur-
Heterogeneous Catalysis and Solid Catalysts 31
sor undergoes transformations in reducing and collapse [63]. It is clear that these complex
oxidizing atmospheres, as shown in the follow- requirements can only be achieved by multicom-
ing scheme [212]: ponent materials.
GRASSELLI [63,213] has listed three key cata-
lytic functionalities required for effective am-
moxidation/oxidation catalysts:
Table 6. Electronic structure of some catalytically active elements and their functionalities [213]
La3þ 2þ 3þ 2
1x Srx Y O31=2x is active for methane cou- Heteropoly compounds can be applied as het-
pling. Other applications of perovskite-type oxi- erogeneous catalysts in their solid state. Their
des in catalysis are in fuel cells, as catalysts for catalytic performance is determined by the
combustion and for DeNOx reactions. primary structure (polyanion), the secondary
structure (three-dimensional arrangement of
Hydrotalcites are another family of solids polyanions, counter cations, and water of crys-
which tolerate rather flexible composi- tallization, etc.), and the tertiary structure (parti-
tions [210,218,219]. Hydrotalcite is a clay miner- cle size, pore structure, etc.) [222,223]. In con-
al. It is a hydroxycarbonate of Mg and Al of trast to conventional heterogeneous catalysts, on
general formula [Mg6Al2(OH)16]CO3 4H2O. which reactions occur at the surface, the reac-
The compositional flexibility of the hydrotalcite tants are accommodated in the bulk of the
lattice permits the incorporation of many different secondary structure of heteropoly compounds.
metal cations and anions to yield solids with the Certain heteropolyacids are flexible, and polar
xþ
general formula ½M2þ 1x Mx ðOHÞ ðA Þx=n
3þ n
molecules are easily absorbed in interstitial
nH2 O (M ¼ Mg ; Ni ; Zn ect.; M3þ ¼
2þ 2þ 2þ 2þ
positions of the bulk solid, where they form a
Al3þ ; Fe3þ ; Cr3þ , etc.; An ¼ CO2 3 ; SO4 ;
2
pseudoliquid phase [222,223].
NO3 , etc.). Hydrotalcites develop large surface Heteropoly compounds develop acidic and
areas and basic properties. They have conse- oxidizing functions, so that they can be used
quently been applied as solid catalysts for base- for acid and redox catalysis. In addition, poly-
catalyzed reactions for fine-chemicals synthe- anions are well-defined oxide clusters. Catalyst
sis, polymerization of alkene oxides, aldol design is therefore possible at the molecular
condensation, etc. Hydrotalcite-type phases level. The pseudoliquid provides a unique reac-
(and also malachite (rosasite)- and copper zinc tion environment.
hydroxycarbonate (aurichalcite)-type phases) Some solid heteropolyacids have high thermal
can also be used as precursors for the synthesis stability and are therefore suitable for vapor-
of mixed oxides by thermal decomposition, for phase reactions at elevated temperatures. The
example, Cu – Zn and Cu – Zn – Cr catalysts thermal stability of several heteropolyacids
[210]. decreases in the sequence H3PW12O40 >
H4SiW12O40 > H3PMo12O40 > H4SiMo12O40
Heteropolyanions are polymeric oxo an- [222,223]. It can be enhanced by formation of
ions (polyoxometalates) formed by condensa- the appropriate salts [224,225].
tion of more than two kinds of oxo an- Because of their multifunctionality, hetero-
ions [220,221]. The amphoteric metals of polyacids catalyze a wide variety of reactions
Groups 5 (V, Nb, Ta) and 6 (Cr, Mo, W) in the including hydration and dehydration, condensa-
þ5 and þ6 oxidation states, respectively, form tion, reduction, oxidation, and carbonylation
weak acids which readily condense to form chemistry with Keggin-type anions of V,
anions containing several molecules of the acid Mo [223,224,226–228]. A commercially impor-
anhydride. Isopolyacids and their salts contain tant process, the oxidation of methacrolein,
only one type of acid anhydride. Condensation is catalyzed by a Cs salt of H4PVMo11O40.
can also occur with other acids (e.g., phosphoric Heteropoly salts with extremely complex
or silicic) to form heteropolyacids and salts. compositions have been proposed, e.g., for the
About 70 elements can act as central heteroa- oxydehydrogenation of ethane. A Keggin-
toms in heteropolyanions. The structures of het- type molybdophosphoric salt with formula
eropolyanions are classified into several families K2P1.2MO10W1Sb1Fe1Cr0.5Ce0.75On was found
according to similarities of composition and to be the most efficient among the tested solids in
structure, such as Keggin type XM12 O40 n , terms of activity, selectivity, and stability [229].
Dawson type X2 M18 O62 n , and Anderson type
XM6 O24 n , where X stands for the heteroatom.
The most common structural feature is the Keg- 4.1.2. Metals and Metal Alloys
gin anion, for which the catalytic properties have
been studied extensively. Typically the M atoms Metals and metal alloys are used as bulk, un-
in catalytic applications are either Mo or W. supported catalysts in only a few cases. Metal
34 Heterogeneous Catalysis and Solid Catalysts
gauzes or grids are used as bulk catalysts in in cubic close-packed (ccp), hexagonal close-
strongly exothermic reactions which require packed (hcp), or simple hexagonal (hex) arrays.
catalyst beds of small height. Typical examples C and N atoms occupy interstitial positions
are platinum – rhodium grids used for ammonia between metal atoms (interstitial alloys). The
oxidation in the nitric acid process [230] and materials have unique properties in terms of
silver grids for the dehydrogenation of methane melting point (> 3300 K), hardness (> 2000 kg
to formaldehyde. mm2), and strength (> 3 105 MPa). Their
Skeletal (Raney-type) catalysts, particularly physical properties resemble those of ceramic
skeletal nickel catalysts, are technologically im- materials, although their electronic and magnetic
portant materials [231] which are specifically properties are typical of metals. Carbon in
applied in hydrogenation reactions. However, the carbides donates electrons to the d band of
their application is limited to liquid-phase reac- the metal, thus making the electronic character-
tions. They are used in particular for the produc- istics of, e.g., tungsten and molybdenum resem-
tion of fine chemicals and pharmaceuticals. Skel- ble more closely those of the platinum group
etal catalysts are prepared by the selective re- metals.
moval of aluminum from Ni – Al alloy particles Bulk carbides and nitrides, e.g., of tungsten
by leaching with aqueous sodium hydrox- and molybdenum, can be prepared with surface
ide [231]. Besides skeletal Ni, cobalt, copper, areas between 100 and 400 m2 g1 by advanced
platinum, ruthenium, and palladium catalysts synthetic procedures [235], so that they can be
have been prepared, with surface areas between applied as bulk catalysts. They catalyze a variety
30 and 100 m2 g1. One of the advantages of of reactions for which noble metals are still
skeletal metal catalysts is that they can be stored preferentially used. Carbides and nitrides are
in the form of the active metal and therefore exceptionally good hydrogenation catalysts,
require no pre-reduction prior to use, unlike and they are active in hydrazine decomposition.
conventional catalysts, the precursors of which Carbides of tungsten and molybdenum are also
are oxides of the active metal supported on a highly active for methane reforming, Fischer –
carrier. Tropsch synthesis of hydrocarbons and alco-
Fused catalysts are particularly used as hols, and hydrodesulfurization, and the nitrides
alloy catalysts. The synthesis from a homoge- are active for ammonia synthesis and hydrode-
neous melt by rapid cooling may yield nitrogenation [234]. The catalytic properties of
metastable materials with compositions that can carbides can be fine tuned by treatment with
otherwise not be achieved [232]. Amorphous oxygen, which leads to the formation of oxy-
metal alloys have also been prepared (metallic carbides [236]. While clean molybdenum car-
glasses) [232,233]. bide is an excellent catalyst for C – N bond
Oxide materials can also be fused for cata- cleavage (cracking of hydrocarbons), molybde-
lytic applications [232]. Such oxides exhibit a num oxide carbide is selective for skeletal
complex and reactive internal interface struc- isomerization [236].
ture which may be useful either for direct cata- In conclusion, carbides and nitrides, espe-
lytic application in oxidation reactions or in cially those of tungsten and molybdenum, may
predetermining the micromorphology of result- well be considered as future substitutes for
ing catalytic materials when the oxide is the platinum and other metals of Groups 8 – 10 as
catalyst precursor. The prototype of such a catalysts.
catalyst is the multiply promoted iron oxide
precursor of catalysts used for ammonia
synthesis [48,234]. 4.1.4. Carbons [237]
1. General). The surface chemistry of carbons is als for proton-exchange membrane fuel cell
rather complex [174,237]. Carbon surfaces may (PEMFC) and direct methanol fuel cell (DMFC)
contain a variety of functional groups, particu- catalysts [241].
larly those containing oxygen, depending on the
provenience and pretreatment of the carbon. At
a single adsorption site several chemically in- 4.1.5. Ion-Exchange Resins and Ionomers
equivalent types of heteroatom bonds may form.
Strong interactions between surface functional Ion-exchange resins (! Ion Exchangers) are
groups further complicate the variety of surface strongly acidic organic polymers which are
chemical structures derived for the most impor- produced by suspension copolymerization of
tant carbon – oxygen system. Two functions of styrene with divinylbenzene and subsequent
the carbon surface act simultaneously during a sulfonation of the cross-linked polymer ma-
catalytic reaction. Firstly, the reactants are che- trix [242]. This matrix is insoluble in water and
misorbed selectively on the carbon surface by organic solvents. Suspension polymerization
ion exchange via oxygen functional groups or yields spherical beads which have different
directly by dispersion forces involving the diameters in the range 0.3 – 1.25 mm. The
graphite valence-electron system. The second Gaussian size distribution of the beads can be
function is the production of atomic oxygen influenced by the polymerization parameters.
occurring on the graphene basal faces of all sp2 A network of micropores is produced during
carbon materials [237]. the copolymerization reaction. The pore size is
Carbon can already be catalytically active inversely proportional to the amount of cross-
under ambient conditions and in aqueous media. linking agent. In the presence of inert solvents
Therefore efforts have been made to apply such as isoalkanes during the polymerization,
carbons as catalysts in condensed phases. Its which dissolve the reactive monomers and pre-
application in the gas phase under oxidizing cipitate the resulting polymers, beads with an
conditions is severely limited by its tendency open spongelike structure and freely accessible
to irreversible oxidation. inner surface are obtained. The matrix is then a
Catalytic applications of carbons include the conglomerate of microspheres which are inter-
oxidation of sulfurous to sulfuric acid, the se- connected by cavities or macropores. Macro-
lective oxidation of hydrogen sulfide to sulfur porous resins are characterized by micropores
with oxygen in the gas phase at ca. 400 K, the of 0.5 – 2 nm and macropores of 20 – 60 nm,
reaction between phosgene and formaldehyde, depending on the degree of cross-linking.
and the selective oxidation of creatinine by air in Strongly acidic polymeric resins are thermal-
physiological environments. ly stable at temperatures below 390 – 400 K.
A potential technological application of car- Above 400 K, sulfonic acid groups are split off
bon catalysts involves the catalytic removal of and a decrease in catalytic activity results.
NO by carbon [237]. Industrially, acidic resins are used in the
More recently, carbon nanotubes (CNT) and production of methyl tert-butyl ether [243].
nanofibers (CNF) have found significant inter- The ionomer Nafion is a perfluorinated poly-
est as catalysts and catalyst supports [237,240]. mer containing pendant sulfonic acid groups
These materials, especially nanotubes, exhibit which is considered to develop superacidic
interesting electronic, mechanical and thermal properties. It can be used as a solid acid catalyst
properties that are clearly different from those of for reactions such as alkylation, isomerization,
activated carbons. High mechanical strength and acylation [244].
and resistance to abrasion in combination with
high accessibility of active sites are advantages
of CNT-based catalysts which make them very 4.1.6. Molecularly Imprinted Catalysts
attractive for liquid-phase reactions, where the [245]
microporosity of activated carbons often limits
the catalytic performance. Due to their high Molecular imprinting permits heterogeneous
electrical conductivity and oxidation stability, supramolecular catalysis to be performed on
CNTs are also highly interesting carrier materi- surfaces of organic or inorganic materials with
36 Heterogeneous Catalysis and Solid Catalysts
substrate recognition. Heterogeneous catalysts are the adsorption of gases such as hydrogen or
with substrate specificity based on molecular methane targeted at the replacement of com-
recognition require a material having a shape- pressed-gas storage, removal of impurities in
and size-selective footprint on the surface or in natural gas, pressure-swing separation of noble
the bulk. The stabilization of transition states by gases (krypton, xenon), and use as catalysts
imprinting their features into cavities or adsorp- [253]. Despite their higher metal content
tion sites by using stable transition-state analo- compared to zeolites, the use of MOFs in
gues as templates is of particular interest. heterogeneous catalysis is restricted due to
Imprinted materials can be prepared on the their relatively low stability at elevated temper-
basis of Al3þ-doped silica gel [246] and of ature and in the presence of water vapor or
cross-linked polymers [247,248]. Chiral molec- chemical reagents. In addition, the metal ions
ular footprint cavities have also been designed in MOFs are often blocked by the organic
and imprinted on the surface of Al3þ-doped linker molecules and are therefore not accessi-
silica gel by using chiral template molecules. ble for catalytic reactions. However, successful
When transition-state or reaction-intermedi- applications of especially stable Pd MOFs
ate analogues are used as templates for molecu- in alcohol oxidation, Suzuki C–C coupling and
lar imprinting, specific adsorption sites are cre- olefin hydrogenation have been reported
ated. Such molecular footprints on silica gel [254]. It can be expected that the number of
consist of a Lewis site and structures comple- successful catalytic studies using MOFs will
mentary to the template molecules. These struc- grow considerably.
tures can stabilize a reacting species in the
transition state and lower the activation energy
of the reaction, thus mimicking active sites of 4.1.8. Metal Salts
natural enzymes and catalytic antibodies.
Although this approach seems to have a high Although salts can be environmentally harmful,
potential for heterogeneous catalysis, the real they are still used as catalysts in some techno-
application of imprinted materials as catalysts logically important processes. FeCl3 – CuCl2 is
still remains to be demonstrated. a catalyst for chlorobenzene production, and
AlCl3 is still used for ethylbenzene synthesis
and n-butane isomerization.
4.1.7. Metal – Organic Frameworks
[249,250]
4.2. Supported Catalysts
Metal – organic frameworks (MOFs) are highly
porous, crystalline solids consisting of a three- Supported catalysts play a significant role in
dimensional network of metal ions attached to many industrial processes. The support provides
multidentate organic molecules. Similar to zeo- high surface area and stabilizes the dispersion of
lites, the spatial organization of the structural the active component (e.g., metals supported on
units gives rise to a system of channels and oxides). Active phase – support interactions,
cavities on the nanometer length scale. A mile- which are dictated by the surface chemistry of
stone for the development of MOFs was the the support for a given active phase, are responsi-
synthesis of MOF-5 in 1999 [251]. This material ble for the dispersion and the chemical state of the
consists of tetrahedral Zn4O6þ clusters linked latter. Although supports are often considered to
by terephthalate groups and has a specific sur- be inert, this is not generally the case. Supports
face area of 2900 m2 g1. MOF-177 has an may actively interfere with the catalytic process.
even larger specific surface area of 4500 m2 Typical examples fortheactive interplay between
g1 [252]. By selection of the linker length, the support and active phase are bifunctional cata-
size of the resulting pores can be tailored. lysts such as highly dispersed noble metals sup-
Due to their extremely high surface areas and ported on the surface of an acidic carrier.
their tunable pore structure with respect to size, To achieve the high surface areas and stabi-
shape, and function, MOFs are highly interest- lize the highly disperse active phase, supports
ing materials for various applications. Examples are typically porous materials having high
Heterogeneous Catalysis and Solid Catalysts 37
thermostability. For application in industrial ity. Although they have not yet found applica-
processes they must also be stable towards the tion in catalysis, the low-weight materials may
feed and they must have a sufficient mechanical well be advantageous supports for high-temper-
strength. ature catalysis processes.
Monolithic supports with unidirectional
macrochannels are used in automotive emission
4.2.1. Supports control catalysts (! Automobile Exhaust Con-
trol) where the pressure drop has to be mini-
Many of the bulk materials described in Section mized [257]. The channel walls are nonporous or
Unsupported (Bulk) Catalysts may also func- may contain macropores. For the above applica-
tion as supports. The most frequently used tion the monoliths must have high mechanical
supports are binary oxides including transitional strength and low thermal expansion coefficients
aluminas, a-Al2O3, SiO2, MCM-41, TiO2 (ana- to give sufficient thermal shock resistance.
tase), ZrO2 (tetragonal), MgO etc., and ternary Therefore, the preferred materials of monolith
oxides including amorphous SiO2 – Al2O3 and structures are ceramics (cordierite) or high-
zeolites. Additional potential catalyst supports quality corrosion-resistant steel. Cordierite is a
are aluminophosphates, mullite, kieselguhr, natural aluminosilicate (2 MgO 2 Al2O3 5
bauxite, and calcium aluminate. Carbons in SiO2). The accessible surface area of these ma-
various forms (charcoal, activated carbon) can terials corresponds closely to the geometric sur-
be applied as supports unless oxygen is required face area of the channels. High surface area is
in the feed at high temperatures. Table 7 sum- created by depositing a layer of a mixture of up to
marizes important properties of typical oxide 20 different inorganic oxides, which include
and carbon supports. transitional aluminas as a common constituent.
Silicon carbide, SiC, can also be used as a This so-called washcoat develops internal sur-
catalyst support with high thermal stability and face areas of 50 to 300 m2/g [258,259].
mechanical strength [255]. SiC can be prepared Silica, MCM-41, and polymers can be func-
with porous structure and high surface area by tionalized for application as supports for the
biotemplating [256]. This procedure yields ce- preparation of immobilized or hybrid cata-
ramic composite materials with biomorphic lysts [174,177,260–266]. The functional groups
microstructures. Biological carbon preforms are may serve as anchoring sites (surface bound
derived from different wood structures by high- ligands) for complexes and organometallic
temperature pyrolysis (1100 – 2100 K) and compounds. Chiral groups can be introduced
used as templates for infiltration with gaseous for the preparation of enantioselective catalysts
or liquid Si to form SiC and SiSiC ceramics. (see Section Hybrid Catalysts).
During high-temperature processing the micro-
structural details of the bioorganic preforms are
retained, and cellular ceramic composites with 4.2.2. Supported Metal Oxide Catalysts
unidirectional porous morphologies and aniso-
tropic mechanical properties can be obtained. Supported metal oxide catalysts consist of at
These materials show low density, high specific least one active metal oxide component
strength, and excellent high-temperature stabil- dispersed on the surface of an oxide support
Al2O3 mostly a and g SA up to 400; thermally stable three-way cat., steam reforming and many other cats.
SiO2 amorphous SA up to 1000; thermally stable; hydrogenation and other cats.
Carbon amorphous SA up to 1000; unstable in oxid. environm., hydrogenation cats.
TiO2 anatase, rutile SA up to 150; limited thermal stability; SCR cats.
MgO fcc SA up to 200; rehydration may be problematic; steam reforming cat.
Zeolites various (faujasites, ZSM-5) Highly defined pore system; shape selective; bifunctional cats.
Silica/alumina amorphous SA up to 800; medium strong acid sites; dehydrogenation cats.; bifunctional catalysts.
SA ¼ surface area in m2/g
38 Heterogeneous Catalysis and Solid Catalysts
[52,267,268]. The active oxides are often transi- deposition of modifiers. The acid strength of
tion metal oxides, while the support oxides aluminas is strongly enhanced by incorporation
typically include transitional aluminas (prefer- of Cl into or on the surface. This may occur
entially g-Al2O3), SiO2, TiO2 (anatase), ZrO2 during impregnation with solutions containing
(tetragonal), and carbons. chloride precursors of an active compo-
Supported vanadia catalysts are extremely nent [169] or by deposition of AlCl3. Chlorinat-
versatile oxidation catalysts. V2O5/TiO2 is used ed aluminas are also obtained by surface reac-
for the selective oxidation of o-xylene to phtha- tion with CCl4 [174]. The presence of chlorine
lic anhydride [269,270] and for the ammoxida- plays an important role in catalytic reforming
tion of alkyl aromatics to aromatic nitriles [270]. with Pt – Al2O3 catalysts [50].
The latter reaction is also catalyzed by V2O5/ Strongly basic materials are obtained by
Al2O3 [270]. The selective catalytic reduction supporting alkali metal compounds on the sur-
(SCR) of NOx emissions with NH3 in tail gas face of alumina [281]. Possible catalysts include
from stationary power plants is a major appli- KNO3, KHCO3, K2CO3, and the hydroxides of
cation of V2O5 – MoO3 – TiO2 and V2O5 – the alkali metals supported on alumina.
WO3 – TiO2 [271,272]. MoO3 – Al2O3 and Sulfation of several oxides, particularly te-
WO3 – Al2O3 (promoted by oxides of cobalt tragonal ZrO2, yields strong solid acids, which
or nickel) are the oxide precursors for sulfided were originally considered to develop superaci-
catalysts (see Section Supported Sulfide Cata- dic properties [282,284], because, like tung-
lysts) for hydrotreating of petroleum (hydrode- stated ZrO2 (see Section Supported Metal Oxide
sulfurization, hydrodenitrogenation, hydro- Catalysts), they also catalyze the isomerization
cracking) [49,273,274]. WO3 – ZrO2 develops of n-alkanes to isoalkanes at low temperature.
acidic and redox properties [275,276]. When
promoted with Fe2O3 and Pt it can be applied as
a highly selective catalyst for the low-tempera- 4.2.4. Supported Metal Catalysts
ture isomerization of n-alkanes to isoalk-
anes [277]. Re2O7 – Al2O3 is an efficient me- Metals typically have high surface free ener-
tathesis catalyst [278]. Cr2O3 – Al2O3 and gies [280] and therefore a pronounced tendency
Cr2O3 – ZrO2 are catalysts for alkane dehydro- to reduce their surface areas by particle growth.
genation and for dehydrocyclization of, e.g., n- Therefore, for applications as catalysts they are
heptane to toluene [279]. generally dispersed on high surface area sup-
The above-mentioned transition metal oxi- ports, preferentially oxides such as transitional
des have lower surface free energies than the aluminas, with the aim of stabilizing small,
typical support materials [52,280]. Therefore, nanosized particles under reaction condi-
they tend to spread out on the support surfaces tions [169, 285]. This can be achieved by some
and form highly dispersed active oxide over- kind of interaction between a metal nanoparticle
layers. These supported oxide catalysts are thus and the support surface (metal – support inter-
frequently called monolayer catalysts, although action:), which may influence the electronic
the support surface is usually not completely properties of the particles relative to the bulk
covered, even at loadings equal to or exceeding metal. This becomes particularly significant for
the theoretical monolayer coverage. This is raftlike particles of monatomic thickness, for
because most of the active transition metal which all atoms are surface atoms. Furthermore,
oxides (particularly those of V, Mo, and W) the small particles expose increasing numbers
form three-dimensional islands on the support of low-coordinate surface metal atoms. Both
surface which have structures analogous to mo- electronic and geometric effects may influence
lecular polyoxo compounds [52,267]. the catalytic performance of a supported metal
catalyst (particle-size effect). Aggregation of
the nanoparticles leads to deactivation.
4.2.3. Surface-Modified Oxides Model supported metal catalysts having uni-
form particle size and structure can be prepared
The surface properties, that is acidity and basic- by anchoring molecular carbonyl clusters on
ity, of oxides can be significantly altered by support surfaces, followed by decarbonyla-
Heterogeneous Catalysis and Solid Catalysts 39
tion [286,287]. Examples are Ir4 and Ir6 clusters Multimetal catalysts Pt – Rh – Pd on Al2O3
on MgO and in zeolite cages. modified by CeO2 as oxygen storage component
Bimetallic supported catalysts contain two are used on a large scale in three-way car
different metals, which may either be miscible exhaust catalysts [259]. Pt supported on chlori-
or immiscible as macroscopic bulk alloys. The nated Al2O3 is the bifunctional catalyst used for
combination of an active and an inactive metal catalytic reforming, isomerization of petroleum
[e.g., Ni and Cu (miscible) or Os and Cu (im- fractions, etc.
miscible)] dilutes the active metal on the particle Modification of supported Pt catalysts by
surface. Therefore, the catalytic performance of cinchona additives yields catalysts for the en-
reactions requiring ensembles of several active antioselective hydrogenation of a-ketoesters
metal atoms rather than single isolated atoms is [290].
influenced [288,289]. Selectivities of catalytic
processes can thus be optimized. Typically, the
surface composition of binary alloys differs from 4.2.5. Supported Sulfide Catalysts
that of the bulk. The component having the lower
surface free energy is enriched in the surface Sulfided catalysts of Mo and W supported on g-
layer. For example, Cu is largely enriched at the Al2O3 or active carbons are obtained by sulfi-
surface of Cu – Ni alloys, even at the lowest dation of oxide precursors (supported MoO3 or
concentration. Also, surface compositions of WO3; see Section Supported Metal Oxide Cat-
binary alloys may be altered by the reaction alysts) in a stream of H2/H2S. They are typi-
atmosphere. cally promoted with Co or Ni and serve (in
In industrial application, supported metal large tonnage) for hydrotreating processes of
catalysts are generally used as macroscopic crude oil, including hydrodesulfurization
spheres or cylindrical extrudates. By special (HDS) [49,273,274], hydrodenitrogenation
impregnation procedures, metal concentration HDN [274], and hydrodemetalation HDM
profiles within the pellet can be created in a [291]. Currently, the CoMoS and NiMoS mod-
controlled way. Examples are schematically els are most accepted for describing the active
shown in Figure 13 [169]. The choice of the phase. These phases consist of a single MoS2
appropriate concentration profile may be crucial layer or stacks of MoS2 layers in which the
for the selectivity of a process because of the promoter atoms are coordinated to
interplay between transport and reaction in edges [49,274], as shown in Figure 14. This
the porous mass of the pellet. For example for figure also indicates that Co may simulta-
the selective hydrogenation of ethyne impurities neously be present as Co9S8 and as a solid
to ethene in a feed of ethene, eggshell profiles solution in the Al2O3 support matrix. It is
are preferred. inferred that the catalytic activity of the MoS2
Applications of supported metal catalysts, layers is related to the creation of sulfur vacan-
such as noble (Pt, Pd, Rh) or non-noble (Ru, cies at the edges of MoS2 platelets. These
Ni, Fe, Co) metals supported on Al2O3, SiO2, or vacancies have recently been visualized on
active carbon include hydrogenation and dehy- MoS2 crystallites by scanning tunneling mi-
drogenation reactions. Ag on Al2O3 is used for croscopy (STM) [292].
ethene epoxidation. Supported Au catalysts are
active for low-temperature CO oxidation.
studied [302,303]. A related novel concept uses formance can be modified in a synergistic man-
solid catalysts with ionic liquid layer (SCILL) as ner by shape selectivity, the electrostatic envi-
a method to improve the selectivity of heteroge- ronment, and the acid-base properties of the
neous catalysts. The sequential hydrogenation of zeolite host. Ligands for metal centers in the
cyclooctadiene to cyclooctene and cyclooctane zeolite cages include ethylenediamine, di-
on a commercial Ni catalyst coated with an ionic methylglyoxime, various Schiff bases, phthalo-
liquid was tested as model system. Compared to cyanines, and porphyrins [305,306]. The en-
the original catalyst, the coating of the internal trapped complexes can be obtained via three
surface with the ionic liquid strongly enhanced principal routers [305]:
the maximum intrinsic yield of the intermediate
product [304]. 1. Reaction of the preformed flexible ligand
with transition metal previously introduced
into the zeolite cages (flexible ligand meth-
4.2.7. Ship-in-a-Bottle Catalysts [305] od). The synthesis of a zeolite entrapped
metal salen complex is schematically shown
Metal complexes which are physically en- in Figure 16.
trapped in the confined spaces of zeolite cages 2. Assembling the ligand from smaller species
(confined catalysts) are known as ship-in-a- inside the zeolite cavities (ship-in-a-bottle
bottle catalysts or tea-bag catalysts. The en- technique). For example, the synthesis of a
trapped complexes are assumed to retain many zeolite-entrapped metal phthalocyanine is
of their solution properties. The catalytic per- schematically shown in Figure 17.
42 Heterogeneous Catalysis and Solid Catalysts
Figure 16. Synthesis of zeolite-entrapped metal salen complexes by the flexible ligand method
3. Synthesis of the zeolite structure around the compounds containing a transition metal such
preformed transition metal complex (zeolite as Ti or V [309,310]. TiCl4 combined with Al
synthesis technique). (C2H5)3 or other alkyl aluminum compounds
were found to be active for olefin polymeriza-
The success of ship-in-a-bottle catalysts in tion. More active catalysts were produced com-
catalytic processes has still to be demonstrated. mercially by supporting the TiCl4 on solid
Zeolite-encapsulated complexes have also MgCl2, SiO2 or Al2O3 to increase the amount
been suggested as model compounds for mim- of active titanium. Currently, Ziegler – Natta
icking enzymes. These zeolite-based enzyme catalysts are produced by ball milling MgCl2
mimics are called zeozymes to describe a cata- with about 5 % of TiCl4, and the cocatalyst is Al
lytic system, in which the zeolite replaces the (C2H5)3.
protein mantle of the enzyme, and the entrapped The Phillips catalyst (! Polyolefins –
metal complex mimics the active site of the Phillips Catalysts) consists of hexavalent sur-
enzyme (e.g., an iron porphyrin) [307]. face chromate on high surface area silicate
Host – guest supramolecular compounds supports. Cr6þ is reduced by ethylene or other
may also be mentioned in this context hydrocarbons, probably to Cr2þ and Cr3þ, the
[245,308]. catalytically active species [309,310].
More recently, so-called single-site catalysts
using metallocenes as active species were devel-
4.2.8. Polymerization Catalysts oped (! Metallocenes, ! Polyolefins)
[310,311]. The activity of these materials is
Ziegler – Natta (! Polyolefins – Ziegler Cat- dramatically enhanced by activation with methy-
alysts) catalysts are mixtures of solid and liquid laluminoxane (MAO), obtained by incomplete
hydrolysis of Al(CH3)3, the catalytic perfor- process companies such as IG Farben and BASF
mance of which is significantly more versatile in Germany, and Standard Oil Company and
than that of the classical Ziegler – Natta or UOP in the USA [320,321]. About ten years
Phillips catalysts. Activities and the nature of later some independent catalyst producing com-
the polymeric product can be tailored by the panies were founded in the USA, Western
choice of the metal and ligands. Europe, and Japan [320]. At present more than
15 international companies [320,322] are pro-
ducing solid catalysts on multitonne scale; for
4.3. Coated Catalysts example:
catalyst production process. Some companies, Table 8. Unsupported catalysts prepared by mechanical treatment
(MT) or by fusion (F)
especially in Western Europe and in the USA,
produce solid catalysts according to ISO Catalyst* Preparation Application
Standard which guarantees a standard catalyst method
quality to the customer [320,324]. Fe2O3(K, Cr, MT ethylbenzene dehydrogenation
Catalysts applied in several industrial Ce, Mo) (styrene production)
processes can be subdivided into the following Fe2O3(K) MT Fischer – Tropsch synthesis
categories: ZnO – Cr2O3 MT hydrogenation of carbonyl
compounds
Fe3O4(K, Al, F NH3 synthesis
*
Unsupported (bulk) catalysts Ca, Mg)
*
Supported catalysts V2O5 – K2S2O7 F SO2 oxidation (H2SO4
production)
Pt/Rh grid F NH3 oxidation (HNO3
5.1. Unsupported Catalysts production)
*
Elements in parentheses are promoters.
Unsupported catalysts represent a large category
and are applied in numerous industrial processes.
Various preparation methods were adopted in the
catalysts based on the fusion of magnetite
past decades in the commercial production of
(Fe3O4) with promoters such as oxides of K,
unsupported catalyst, such as mechanical treat-
Al, Ca, and Mg [232]. Another example is the
ment or fusion of catalyst components, precipi-
preparation of SO2 oxidation catalysts by fusion
tation, coprecipitation, flame hydrolysis, and
of V2O5 with K pyrosulfate (K2S2O7) [232].
hydrothermal synthesis[232,322,325–329].
Some producers incorporate Cs oxide as an
Mechanical treatment, for example, mix- activity promoter in this catalyst.
ing, milling, or kneading of catalytic active Quite recently, amorphous alloys composed,
materials or their precursors with promoters, e.g., of Pd and Zr, so-called metallic glasses
structure stabilizers, or pore-forming agents, is were found to be active in catalytic
one of the simplest preparation meth- oxidations [232,233].
ods [322,325–327]. In some cases, however, the Industrial catalysts produced by the fusion
required intimate contact of catalyst compo- process are listed in Table 8.
nents could not be achieved and therefore the
activity, selectivity, or thermal stability of cat- Precipitation and coprecipitation are the
alysts prepared in this way was lower than of most frequently applied methods for the prepa-
those prepared by other methods. However, ration of unsupported catalysts or catalyst sup-
recent improvements in the efficiency of various ports [322,325–329]. However, both methods
aggregates for the mechanical treatment of so- have the major disadvantage of forming large
lids resulted in activity enhancement. An im- volumes of salt-containing solutions in the pre-
portant advantage of these methods is that for- cipitation stage and in washing the precipitate.
mation of wastewater is avoided. Source materials are mainly metal salts, such
Industrial catalysts produced by mechanical as sulfates, chlorides, and nitrates. Acetates,
treatment are summarized in Table 8. formates, or oxalates are used in some cases.
In industrial practice nitrates or sulfates are
Fusion of components or precursors is preferred. Basic precipitation agents on an in-
used for the production a small group of unsup- dustrial scale are hydroxides, carbonates, and
ported catalysts. The fusion process [232] per- hydroxocarbonates of sodium, potassium, or
mits the synthesis of alloys consisting of ele- ammonium.
ments which do not mix in solution or in the Alkali metal nitrates or sulfates formed as
solid state. However, preparation of unsupport- precipitation byproducts must be washed out of
ed catalysts by fusion is an energy-consuming the precipitate. Thermally decomposable an-
and quite expensive process. ions, such as carbonates and carboxylates and
The most important application of this meth- cations like NH4 þ are especially favored in
od is the production of ammonia synthesis catalyst production.
Heterogeneous Catalysis and Solid Catalysts 45
Coprecipitation of two or more metal cations concentrations of the solutions, higher tempera-
is a suitable operation for the homogeneous tures, and extended ageing provide coarse crys-
dispersion of the corresponding oxides, espe- talline precipitates which are easier to purify
cially if the catalyst precursors have a defined and separate [322,325–329].
crystalline structure, for example, Cu(OH) The industrial production of precipitated
NH4CrO4 or Ni6Al2(OH)16CO3. After thermal catalysts usually involves the following steps:
treatment, binary oxides such as CuO – Cr2O3
*
and NiO – Al2O3 are formed [322,325–329]. Preparation of metal salt solution and of
Precipitation and coprecipitation can be car- precipitating agent (dissolution, filtration)
*
ried out in batch or continuous operations. Precipitation
*
If the metal salt solution is placed in the Ageing of the precipitate
*
precipitation vessel and the precipitating agent Washing of the precipitate by decantation
*
is added, then the pH changes continuously Filtration
*
during the precipitation. Coprecipitation should Washing of the filter cake (spray drying)
*
be carried out in the reverse manner (addition of Drying
*
the metal salt solution to the precipitation agent) Calcining
*
to avoid sequential precipitation of two or three Shaping
*
metal species. Activation
If the metal salt solution and the precipitating
agent are simultaneously introduced into the Operations such as filtration, drying, calci-
precipitation vessel, then it is possible to keep nation etc. are discussed in Section Unit Opera-
the pH constant. However, the residence time of tions in Catalyst Production.
theprecipitate in thevesselchanges continuously. Typical unsupported industrial catalysts pro-
Finally, if the metal salt solution and the pre- duced by precipitation or coprecipitation are
cipitating agent are continuouslyintroduced in the compiled in Table 9.
precipitation vessel, and the reaction products are
removed continuously, then pH and residence The sol – gel process [330] involves the
time can be kept constant [322,325–329]. formation of a sol, followed by the creation of a
Besides pH and residence time, other pre- gel. A sol (liquid suspension of solid particles
cipitation parameters, such as temperature, agi- smaller than 1 mm) is obtained by the hydrolysis
tation, and concentration of starting solutions, and partial condensation of an inorganic salt or a
affect the properties of the precipitate. The metal alkoxide. Further condensation of sol
choice of anions, the purity of raw material, particles into a three-dimensional network re-
and the use of various additives also play an sults in the formation of a gel. The porosity and
important role [322,325–329]. the strength of the gel are strongly affected by
In general, highly concentrated solutions, conditions of its formation. For example, slow
low temperatures and short ageing times result coagulation, elevated temperature, or hydro-
in finely crystalline or amorphous materials thermal posttreatment increase the crystalline
which are difficult to wash and filter. Lower fraction of the gel.
Table 10. Catalysts (their precursors) or supports prepared by sol – gel process (SG), flame hydrolysis (FH), or thermal decomposition (TD) of
inorganic metal complexes
general, with increasing acid strength the metal Heterogenization of homogeneous cata-
ions are forced deeper into the support lysts is based on the binding of metal
particles [322]. complexes to the surface or entrapment in pores
of the inorganic or organic support [266]. Such
Ion exchange [169,322] is very similar to catalysts are used mainly in stereospecific hy-
ionic adsorption but involves exchange of ions drogenations in the production of fine chemicals
other than protons. Lower valence ions, such as or pharmaceuticals.
Naþ or NHþ 4 can be exchanged with higher Enzymes [266] can also be heterogenized.
valence ions, for example, Ni2þ or Pt4þ. This They found industrial application in biochemi-
method is used mainly in the preparation of cal processes. A prominent example is the
metal-containing zeolites, e.g., Ni- or Pd-con- isomerization of glucose to fructose in the pro-
taining Y zeolites or mordenites used in petro- duction of soft drinks.
leum-refining processes.
Drying Because drying conditions such as Physical and mechanical properties and pore
rate, temperature, duration, or gas flow rate can structures can also change. The calcination
change the physical properties of the resulting temperature is usually slightly higher than that
material, it is important to measure and keep of the catalyst operating temperature
these parameters constant. For example the [322,325,328,335].
porosity of precipitated catalysts depends on For the calcination of powder or granulate,
the drying procedure. The drying of impregnat- rotary kilns are preferably used [325,328].
ed supports can change the distribution of active Smaller batches of powdered catalysts are cal-
components. Their uniform distribution can be cined in box or muffle furnaces with trays, as in
obtained only if all the liquid is evaporated the case of drying. The gases that are mainly
spontaneously [322,325,328]. Usually, drying used for heating are in direct contact with the
proceeds up to 400 K. material being calcined [322,325,328].
For the drying of filter cake, various tools are Pellets or extrudates are calcined in belt or
used, e.g., box furnaces with trays, drum dryers, tunnel furnaces. The tunnel-type calciner can
rotary kilns, and spray dryers [322,325,328]. operate at substantially higher temperatures
The main problems with drums and rotary (close to 1270 – 1470 K) than the belt type
dryers are the feeding of the wet filter cake and (870 – 1070 K). The tunnel calciner is especial-
removal of adhering material from the walls. ly suitable for firing ceramic carriers. The ma-
Because lumps are usually formed in the drying terial being calcined is taken in boxes or carts
process, the resulting material must pass a gran- which are recycled to the entrance via a contin-
ulator equipped with a sieve [328]. uous chain or belt [328].
Spray dryers provide microspherical materi-
als with a narrow particle-size range. Spray Reduction, Activation, and Protection
dryers are equipped with a nozz1e or a rotating Reduction, activation, or passivation, is in sev-
disk to disperse the watery slurry of the filter eral cases the last step in catalyst production.
cake in a stream of hot air [322,328,335]. These operations are performed by the catalyst
All the above drying equipment operates in producer or in the plant of the client.
continuous mode. For example, in the production of Ni cata-
Small batches of catalyst precursors are dried lysts for the liquid-phase hydrogenation of fats
in box furnaces with trays [325]. and oils, the reduction of NiO deposited on
For the drying of extrudates, continuously kieselguhr is carried out exclusively by the
operating belt dryers have found technical catalyst producer. The reduction of powders
application [328]. (50 – 500 mm particle size) is performed on
an industrial scale in fluid-bed reactors. The
Calcination The main object of calcina- reduced material is pyrophoric and must be
tion (thermal treatment in oxidizing atmo- protected with a hard fat such as tallow, to
sphere) is to stabilize physical and chemical make its handling easy and safe. The finished
properties of the catalyst or its precursor. During catalyst is supplied in the form of flakes or
calcination, thermally unstable compounds pastilles [322,328,336].
(carbonates, hydroxides, or organic com- The reduction of metal oxides such as NiO,
pounds) decompose and are usually converted CuO, CoO, or Fe2O3 is carried out with H2 at
to oxides. During calcination new compounds elevated temperature (> 470 K) and has two
may be formed, especially if the thermal treat- steps. In the first step metal nuclei are formed.
ment is carried out at higher temperatures [268]. In the second, nuclei accumulate to form metal
For example, in the thermal decomposition of crystallites. The rates of both processes de-
Cu or Ni nitrate deposited on alumina, not only pend on temperature and on the nature of the
CuO or NiO but also Cu or Ni aluminate is substrate [322]. Reduction at lower tempera-
additionally formed [268]. tures (< 570 K) provides a narrow distribu-
Furthermore amorphous material can be- tion of small metal crystallites. Reduction at
come crystalline. Various crystalline modifica- higher temperatures (> 670 K) gives a broad-
tions can undergo reversible or irreversible er distribution and larger metal crystallites
changes. [322].
Heterogeneous Catalysis and Solid Catalysts 51
Reduction of some oxides, such as those of Spheres consisting of Al2O3, SiO2, or alu-
Cu and Fe, is exothermic and needs to be carried minosilicate with 3 – 9 mm diameter are used
out carefully with H2 diluted with N2. preferentially as a support for catalysts in
Water, the reduction product, has negative moving-bed or ebullating-bed reactors. They
effects on the rate and on the extent of reduc- are produced by the so-called oil-drop method
tion [322]. In industrial practice, where H2 is (see Section Unsupported Catalysts). Spheres
recycled, the removal of water by freezing out prepared in this way possess sufficient abrasion
(below 270 K) and by adsorption on molecular resistance [322,328,335].
sieve is essential. Another method for producing spheres is
To achieve optimal activity, partial reduction based on agglomeration of powder by moistening
of oxidic catalysts is common [322,337]. For on a rotating disk (spherudizer) [322,328,335]. As
example, Ni catalysts for fat and oil hydrogena- the spheres reach the desired diameter they are
tion contain about 50 – 60 wt % of metallic Ni, removed automatically and transported to the
45 – 35 wt % NiO, and about 5 wt % Ni dryer and calciner. Such spheres are suitable for
silicate. fixed bed reactors.
When the reduction of shaped oxidic cata- Other methods for forming spherical parti-
lysts is conducted by the catalyst producer, then cles include tumbling short, freshly extruded
the active material is protected either with a cylinders in a rotating drum [328].
high-boiling liquid such as higher aliphatic In the briquetting technique, the plastic mix-
alcohols or C14 – C18 paraffins [337] or it is ture of catalyst powder with a binder is fed
passivated. In this procedure, chemisorbed hy- between two rotating rolls provided with hol-
drogen is removed in a gas stream composed of lowed-out hemispheres [328].
N2 and about 0.1 – 1.0 vol % of O2 at ambient Extrusion of pastes containing catalyst pow-
temperature. After this treatment catalysts can der, binders and lubricants is a frequently used
be handled in air without any precautions [336]. industrial shaping method [322,328,335].
The activity is restored in the client’s plant by Depending on the properties of the paste, press
treatment with H2 [322]. or screw extruders are applied. Press extruders
The activation of hydrotreating catalysts are principally suitable for viscous pastes.
composed of Ni- or Co-promoted MoO3 – Screw extruders are preferred for thixotropic
Al2O3 is carried out with H2 containing masses. In both cases, pastes are forced through
10 vol % of H2S [268]. In the past, this activa- a die, and the extruded material is cut with a
tion was performed exclusively in the hydro- special device to a desired length and falls onto a
desulfurization plants. However, presulfiding at moving belt that transports it through a drier or
catalyst producers is becoming more common calciner [322,328,335]. Poly(vinyl alcohol),
[322]. powdered stearine, and Al stearate are used as
Mainly electrical or gas-heated shaft reactors lubricants. If the mass being extruded contains
are used for the reduction of extrudates, spheres, alumina, then peptizing agents such as nitric
or pellets in plants of catalyst producers. acid are added mainly to improve the mechani-
cal strength [322,327,328].
Catalyst Forming The size and shape of Another type of binder is calcium aluminate
catalyst particles depend on the nature of the cement, which sets up by treatment with
reaction and on the type of applied reactor. steam [322,328].
Reactions in the liquid phase require small The extruded material can have different
particles or even powders (50 – 200 mm). Such shapes, such as cylinders (noodles), hollow
materials are made by grinding of a dried or cylinders (macaroni), or ribbed cylinders. The
calcined precursor, e.g., filter cake, using gran- sizes depend on the shape and are in the range of
ulators equipped with sieves to give uniform 1.5 – 15 mm diameter [328,337].
particle size [322,328,335,337]. Added organic lubricants and pore-forming
Catalysts for fluidized bed reactors (0.05 – agents can be removed by calcination in a
0.25 mm) are usually made by spray drying or stream of air.
by cooling molten material droplets (V2O5) in Special extrusion techniques and equipment
an air stream [322,328,335]. are necessary to produce honeycombs.
52 Heterogeneous Catalysis and Solid Catalysts
Extruding is less expensive than pelletizing, according to the state of aggregation of the
but extrudates have less resistance to abrasion catalyst precursor [338].
than pellets. Extrudates are suitable for different Gaseous catalyst precursors can be trans-
types of fixed-bed reactors operating in the gas formed into coatings by chemical vapor depo-
or trickle phase. sition (CVD) or physical vapor deposition
Pelletizing is a very common method for (PVD). Coating methods based on a liquid phase
catalyst forming. It is based on compression of comprise sol – gel methods, deposition of cat-
a certain volume of powder in a die between two alyst suspensions, and combinations of both
moving punchers, one of which also serves to techniques. Depending on the adjusted viscosity
eject the formed pellet [322,328,335]. Depend- of the sols or suspension, the liquid precursors
ing on the size and the shape of the prepared may be applied on surfaces by dip coating,
pellets, the material being pelletized must be spraying, printing, or rolling. Solid catalyst
crushed and forced through a corresponding powders can be applied, e.g., by flame spray
sieve [328]. Furthermore, lubricants such as deposition or powder plasma spraying.
graphite, Al stearate, pol(vinyl alcohol), kaolin, A coating procedure that has been intensive-
and bentonite are added before the material ly studied is the manufacture of monoliths, e.g.,
enters the tabletting machine. The fluidity of as catalysts for pollution control [340]. Oxides
the material is required to assure homogeneous such as Al2O3, CeO2, and ZrO2 (washcoat) are
filling of the die [322,328,335]. As in the case of deposited on monoliths with a honeycomblike
extrudates, organic lubricants can be removed structure by dipping into an aqueous slurry
by calcination of the pellets. containing primary particles (about 20 nm in
Industrial pelleting machines are equipped diameter) of these materials [259]. The excess
with around thirty dies and produce about 10 li- slurry is blown out, and after drying and calci-
ter of pellets per hour or more, depending on nation a thin catalyst layer is obtained, the
their shape and size. Pressures in the range 10 – thickness of which can be tailored by adjusting
100 MPa in the pelleting machine are the slurry properties and repetition of the dip-
common [322,328,335]. coating step.
Commercially, cylindrical pellets with sizes
such as 3 3, 4.5 4.5, 5 5, or 6 6 mm
are offered [322,328,335]. Production of 3 3 6. Characterization of Solid
mm pellets is more expensive than that of larger Catalysts
sizes. Besides cylindrical pellets, various com-
panies provide rings, cogwheels, spoked Catalytic activity and selectivity critically de-
wheels, multihole pellets, etc. [336,337]. pend on the morphology and texture, surface
Pellets of different shapes and sizes are suit- chemical composition, phase composition, and
able for various types of fixed-bed reactors. structure of solid catalysts. Therefore, many
physical and chemical methods are used in ca-
Coating of inert supports [338] with a thin talysis research to characterize solid catalysts
layer of catalytically active material is required and to search for correlations between structure
for manufacture of coated catalysts. A variety of and performance of catalysts. These methods
methods for coating with catalysts are available. include classical procedures [341] as well as
One can distinguish between material-depen- techniques developed more recently for the study
dent methods for the preparation of thin catalyt- of the chemistry and physics of surfaces [341].
ically active layers on supports and material-
independent coating methods [319]. Material-
dependent methods are anodic oxidation of 6.1. Physical Properties
aluminum or aluminum alloys, which gives rise
to a layer with a one-dimensional and unidirec- 6.1.1. Surface Area and Porosity
tional pore system with adjustable proper- [342,343]
ties [339], and formation of porous layers on
FeCrAl alloys by heat treatment. Material-in- The specific surface area of a catalyst or support
dependent coating technologies can be grouped (in m2/g) is determined by measuring the vol-
Heterogeneous Catalysis and Solid Catalysts 53
ume of gas, usually N2, needed to provide a od [345] and the as-method [346]. In the origi-
monomolecular layer according to the Bru- nal t-method the amount of nitrogen adsorbed at
nauer – Emmett – Teller (BET) method. 77 K was plotted against t, the corresponding
In this approach, the determination of the multilayer thickness calculated from a universal
monolayer capacity is based on the physisorp- N2 isotherm, while in the as method the multi-
tion of the test gas. The volume adsorbed at a layer thickness t is replaced by the reduced
given equilibrium pressure can be measured by adsorption as. Here, as is defined as the dimen-
static methods, namely, volumetric or gravimet- sionless adsorption na =nax such that as ¼ 1 at p/
ric measurements. Flow or dynamic techniques po ¼ 0.4, and na is the adsorbed amount in
are also applied. moles of the adsorbate (e.g., N2) at a given
The total surface area of a porous material is relative pressure and nax is the amount adsorbed
given by the sum of the internal and external (in moles) at a relative pressure of 0.4.
surface areas. Pores are classified as micropores For meso- and macroporous materials (pore
(pore width < 2 nm), mesopores (pore width width > 2 nm), the pore size distribution is
2 – 50 nm), and macropores (pore width > 50 determined by measuring the volume of mercu-
nm) according to IUPAC definitions [344]. ry (or another nonwetting liquid) forced into the
The specific pore volume, pore widths, and pores under pressure [322]. The measurement,
pore-size distributions for micro- and mesopores carried out with a mercury pressure porosimeter,
are determined by gas adsorption. For meso- depends on the following relation:
pores, the method is based on the dependence
2ps cosa
of the pressure of capillary condensation on the P¼ ð19Þ
radius of a pore in which condensation takes rp
place, which is given by the Kelvin equation: where P is pressure, s is surface tension of
V 2s cosu mercury, and a is the contact angle of mercury
lnðp=po Þ ¼ ð18Þ with solid. At pressures of 0.1 – 200 MPa, pore
RT rk
size distributions in the range of 3.75 –
where p/po ¼ pressure/saturation pressure, V is 7500 nm can be measured. Because the actual
the molar volume, s the surface tension of the shape of the pores is not exactly cylindrical as
liquid adsorbate, Q the contact angle between assumed in the derivation of the above equation,
adsorbate and adsorption layer on pore walls the calculated pore sizes and distributions can
(hence, Q ¼ 0 is a good approximation), and deviate appreciably from the actual values
rK is Kelvin radius of a pore assuming cylindrical shown by electron microscopy.
shape. Since an adsorption layer is typically For pore systems with narrow pore size dis-
formed before capillary condensation occurs, tributions, the average pore radius can be ap-
the geometric radius rp of a pore is given by the proximated by using
sum of the Kelvin radius rK and the thickness of
rp ¼ 2 Vp =Sp ð20Þ
the adsorption layer t: rp ¼ rK þ t. Mesopore
size distributions can be calculated when adsorp- where Vp is pore volume, and Sp is the surface
tion and desorption isotherms are available in the area. The pore volume of a catalyst or support is
full pressure range up to p/po ¼ 0.95. The given by
mesopore volume Vp is assumed to be complete-
ly filled at this relative pressure, which corre- Vp ¼ 1=rp 1=r ð21Þ
sponds to rp 20 nm.
where rp and r are the particle and true densi-
In the micropore range (pore width < 2 nm), ties, respectively. The former is determined by a
where the pore dimensions are comparable to pycnometer using a nonpenetrating liquid, such
molecular dimensions, pore filling occurs rather as mercury, whereas the true density is obtained
than condensation [343]. The Dubinin – Ra- by measuring the volume of the solid part of a
dushkevich and the Dubinin – Stoeckli theories weighed sample by helium displacement.
then permit the estimation of pore dimensions In certain instances, pore dimensions can be
from physisorption data. In addition, several determined by high-resolution electron micros-
empirical methods exist, such as the t-meth- copy (HREM) [347].
54 Heterogeneous Catalysis and Solid Catalysts
6.1.2. Particle Size and Dispersion [348] phases present in a catalyst [349,354]. It is based
on the comparison of the observed set of reflec-
The surface area of active metals dispersed on a tions of the catalyst sample with those of pure
support deserves particular consideration since reference phases, or with a database (Powder
the metal surface area and particle size (which Diffraction File (PDF) distributed by ICDD, the
are interrelated quantities) determine the cata- International Centre for Diffraction Data). XRD
lytic properties of supported metal catalysts. studies can now be carried out in situ on the
The metal dispersion D is given by D ¼ NS/NT, working catalyst [354], and the use of synchro-
where NS is the number of metal atoms exposed tron radiation permits dynamic experiments in
at the surface and NT is the total number of metal real time [355]. Time-resolved studies on a
atoms in a given amount of catalyst. The fraction timescale of seconds are now becoming possi-
of surface atoms D can be determined if NS is ble. Quantification of phase compositions can
experimentally available. It can be determined also be performed.
by chemisorption measurements with adsorp- More sophisticated analysis of the diffraction
tives that strongly bind to the metal but which patterns of crystalline materials provides de-
interact negligibly with the support at the chosen tailed information on their atomic structure. The
temperatures and pressures. H2, CO, NO, and Rietveld method is used for structure refine-
N2O have been used for this purpose at or above ments. Perhaps more importantly for catalytic
room temperature [348], and static, dynamic, materials, the local atomic arrangement of
and desorption methods have been applied. amorphous catalysts is based on the Debye
Saturation values of the chemisorbed amounts equation, which gives the intensity scattered by
permit NS to be calculated if the chemisorption a collection of randomly distributed atoms. The
stoichiometries are known. Fourier transform of the Debye equation gives
Dispersion is directly related to particle size the radial distribution function (RDF) of elec-
and particle size distribution. Assuming reason- trons, from which the number of atoms (elec-
able model shapes for the metal particles, aver- trons) located in the volume between two
age particle sizes can be calculated from the spheres of radius r and r þ dr around a central
chemisorption data. atom, i.e., the radial density of atoms, can be
Average crystallite size distributions can be obtained [354]. This approach has been applied
determined independently from X-ray diffrac- for the structural analysis of amorphous or
tion line broadening [348,350], and small-angle poorly crystalline catalyst materials and of
X-ray scattering (SAXS) permits the determi- small metal particles.
nation of particle sizes and particle size distri- X-ray Absorption Spectroscopy (XAS)
butions, but also of the specific surface area of [356,358], is the method of choice where the
the metal and of the support [348,350]. applicability of XRD for structure analyses
Electron microscopy offers the unique ceases to be possible. Because of their high
opportunity to observe catalyst morphologies photon flux, synchrotron facilities are the pre-
over the entire range of relevant particle ferred sources for XAS experiments. The physical
sizes [347,348,351–353]. Particle shapes and principle of XAS is the ejection of a photoelec-
sizes of the support or active phase and their tron from a core level of an atom by absorption of
size distributions can be extracted from micro- an X-ray photon. The position of the absorption
graphs, but structural information can be also edge gives the binding energy of the electron in
obtained by electron-diffraction and lattice- the particular core level and is thus characteristic
imaging techniques [347]. of the respective element and its chemical state
(see also ! Surface and Thin-Film Analysis)
and the shape of the absorption edge provides
6.1.3. Structure and Morphology information on the distribution of the local den-
sity of states (LDOS).
X-ray powder diffraction (see also ! The ejected photoelectron wave is backscat-
Structure Analysis by Diffraction – Diffraction tered at neighboring atoms, and the scattered
by Polycrystalline Specimens) (XRD) is a wave interferes with the outgoing primary wave.
routine technique for the identification of This interference results in a modulation of the
Heterogeneous Catalysis and Solid Catalysts 55
spectroscopy (EDS) is sensitive for elements tigations pressed self-supporting wafers have to
with atomic numbers Z > 11. For lighter ele- be used. Samples which exhibit only weak bulk
ments (Z < 11), electron energy loss spectros- absorption, and the average particle size d of
copy EELS is applied. which is smaller than the wavelength of the
Controlled atmosphere electron microscopy infrared radiation (d < l) are optimally suited
(CAEM) [347,361] is arousing considerable for the transmission mode. Transmission – ab-
interest as it will permit the observation of sorption infrared spectroscopy has been partic-
changes in the catalyst structure and morpho- ularly successful in elucidating the structure of
logy under reaction conditions. hydroxyl groups [174,362]. More strongly ab-
sorbing materials, and particularly those having
Vibrational Spectroscopy [362] (! In- average particle sizes greater than the wave-
frared and Raman Spectroscopy). Vibrational length of the infrared radiation, which therefore
spectroscopy is one of the most promising and cause significant scattering losses in transmis-
most widely used methods for catalyst charac- sion, may preferentially be studied by diffuse
terization, since it provides detailed structural reflectance spectroscopy (DRS, DRIFT). A
information on the solid catalyst material and on powerful technique for structural studies on
surface groups and adsorbates. Several vibra- catalytic materials under extreme temperature
tional spectroscopic methods can be applied in and pressure conditions is laser Raman spec-
situ, and they can be successfully used for studies troscopy (LRS), although laser heating and
on ill-defined high surface area porous materials. laser-induced fluorescence may cause serious
In situations where X-ray diffraction techniques problems. One way, among others [362], to
are not applicable, vibrational spectroscopy can avoid fluorescence is to use of UV light instead
often provide information on phase transitions of visible radiation for spectral excitation [363].
and changes in compositions of bulk catalyst LRS has been successfully applied for the struc-
materials, on their crystallinity, and on the nature tural characterization of complex oxides, zeo-
of surface functional groups. Most vibrational lites, and supported oxides and sulfides [362].
spectroscopic methods are not surface-sensitive, Surface-enhanced Raman spectroscopy (SERS)
but they become surface-sensitive when vibra- has found some application in studies of finely
tional spectra are recorded for groups or divided metal catalysts, particularly silver [364].
adsorbates that are present exclusively at the Second harmonic generation (SHG) and sum
material’s surface. Representative examples for frequency generation (SFG) [365,366] are non-
the structural characterization of solid catalysts linear optical techniques with high surface sen-
by vibrational spectroscopy are bulk oxides (in- sitivity which will probably find increasing
cluding simple binary oxides, multicomponent application in studies relevant to catalysis.
materials such as oxidation catalysts, and zeo-
lites and molecular sieves), and supported oxides Neutron techniques [367] include neu-
(e.g., monolayer-type catalysts), and sulfides. tron diffraction and inelastic neutron scattering
The vibrational analysis of surface groups, par- (INS). Both techniques are particularly sensitive
ticularly of hydroxyl groups, can also be ad- to light elements (such as H or D) and provide
dressed. In many cases surface hydroxyl groups complimentary structural information to XRD.
(e.g., on oxides) are simply formed by dissocia-
tive chemisorption of water molecules, which
reduces the surface free energy. Hydroxyl groups 6.1.4. Local Environment of Elements
can also be constituents of the solid-state struc-
ture, for example as in zeolites. Nuclear spectroscopic methods provide infor-
There are several methods and techniques of mation on the local environment of several
vibrational spectroscopy which are particularly selected elements.
suitable in catalysis research. Infrared transmis-
sion – absorption spectroscopy is the most M€ ossbauer spectroscopy and time differen-
commonly used technique. The KBr disk tech- tial perturbed angular correlation
nique is routine for transmission spectroscopy (TDPAC) belong to the class of techniques
of powder samples. However, for in situ inves- which detect solid-state properties mediated by
Heterogeneous Catalysis and Solid Catalysts 57
hyperfine interactions via nuclear spectrosco- dipolar interactions, chemical shift interactions,
py [368]. Both techniques are g spectroscopies; quadrupolar interactions (for nuclei with spin
they are bulk techniques and can be applied I > 1/2) contribute strongly to the shape and
under in situ conditions, although M€ ossbauer position of NMR lines. Because of their struc-
spectroscopy requires low temperatures. ture-dependence these interactions are the main
M€ossbauer spectroscopy (M€ ossbauer Spec- source of information on the structural environ-
troscopy) [368,369] provides information on ment of the nucleus in question. The selective
oxidation states, phases, lattice symmetry, and determination of the related interaction para-
lattice vibrations. Its application is limited to meters of structurally inequivalent nuclei is the
elements which exhibit the M€ ossbauer effect, major goal of an NMR experiment. In well-
such as iron, cobalt, tin, iridium, ruthenium, crystallized samples, the interaction parameters
antimony, and platinum. Particularly valuable adopt unique values, while in poorly crystal-
information on catalyst structures has been ob- lized or amorphous powders they must be
tained for iron catalysts for Fischer-Tropsch and described by distribution functions.
ammonia synthesis, and for cobalt-molybde- The anisotropy of the above-mentioned inter-
num hydrodesulfurization catalysts. actions results in line broadening, and the spectra
The time differential observation of the per- of polycrystalline samples consist of a broad
turbed angular correlation of g rays emitted from superposition of signals arising from different
radioactive nuclei (TDPAC) [368,370,371] is a orientations of the crystallites relative to the
g-spectroscopic technique which also allows the direction of the external magnetic field Bo,
determination of hyperfine interactions such as weighted by the statistical probability with
nuclear electric quadrupole interactions (NQI). which each orientation occurs (powder patterns).
The NQI parameters enable local structural in- Special techniques have been developed which
formation around the g emitter to be extracted. remove or at least reduce substantially these line-
The technique has been successfully applied in broadening effects and permit highly resolved
studies on molybdenum-containing catalysts, NMR spectra of powders with individual lines
and its application to tungsten seems promising. for inequivalent nuclei to be recorded. The most
important of these techniques are dipolar decou-
Solid State Nuclear Magnetic Resonance pling, magic-angle spinning (MAS), and double
[372–374] (see also ! Nuclear Magnetic oriented rotation (DOR). Cross-polarization
Resonance and Electron Spin Resonance Spec- (CP) improves the sensitivity for nuclei with
troscopy – NMR of solids and Heterogeneous low natural abundance and allows the spatial
Systems). NMR spectroscopy in heterogeneous proximity of nuclei to be monitored.
catalysis principally allows the characterization Typical examples for structural characteriza-
of the chemical and structural environment of tions by solid-state NMR [372] are studies on
atoms in the catalysts (or in species adsorbed on zeolites using 27Al and 29Si NMR. Information
catalyst surfaces). NMR studies on catalysts can on the distribution of Al in the environment of Si
be carried out over a wide range of temperatures atoms and on the possible presence of nonfra-
and pressures, as well as in the presence of gases mework Al species has been obtained. The
and liquids. Information can therefore be derived location of exchangeable alkali metal ions has
about the structures of catalysts and their been studied by 23Na and 133Cs NMR. Vanadi-
thermal or chemical transformations. In addi- um- and molybdenum-based catalysts have suc-
tion, specific adsorbent – adsorbate interac- cessfully been characterized by 51V and 95Mo
tions, the nature of chemically bonded surface NMR.
species, and chemical reactions occurring at the
catalyst surface can be studied. Most elements of
interest in catalysis have isotopes that can be 6.2. Chemical Properties
studied with modern NMR spectrometers. Iso-
tope enrichments may be desirable or even nec- 6.2.1. Surface Chemical Composition
essary for certain elements, for example, 17 O.
NMR spectra of solids are often complex The atomic composition of a catalyst surface
since structure-dependent interactions such as plays a decisive role for the catalytic properties.
58 Heterogeneous Catalysis and Solid Catalysts
Electron and ion spectroscopies [375] are sur- the kinetic energy Ek of the emitted photoelec-
face-sensitive analytical tools which provide trons is measured. The energy balance is given
information on the atomic composition within by:
the topmost atomic layers. The information Ek ¼ hnEb F ð22Þ
depth, i.e., the number of atomic layers contrib-
uting to the measured signal, depends on the This equation permits the electron binding
method. Concentration profiles can be obtained energy Eb (relative to the Fermi level) to be
by sputter etching of the surface by ion bom- measured when the photon energy hn and the
bardment. The application of these particle work function F of the spectrometer are known.
spectroscopies requires ultrahigh-vacuum The binding energies are characteristic for a
(UHV) conditions. particular element.
The basis for the identification of atoms on As a result of the photoionization a singly
surfaces of solid materials by electron spectro- ionized atom is formed, which can also be
scopies, such as Auger electron spectroscopy produced by electron impact. The core hole
(AES) and X-ray photoelectron spectroscopy (e.g., in the K shell) can be filled by an electron
(XPS) are the electronic binding energies. With from a higher shell (e.g., the L1 shell) and the
ion spectroscopies, such as low-energy ion scat- energy of this de-excitation process can be
tering (LEIS) and Rutherford backscattering released by emission of an X-ray photon (X-ray
(RDS), surface atoms are identified by their fluorescence, XRF) or can be transferred to
nuclear masses. Ion bombardment of surfaces another electron (e.g., in the L2 shell) which is
is accompanied by sputtering processes (surface then emitted with a well-defined kinetic energy
etching) which lead to the removal of secondary (Auger process). This kinetic energy is deter-
ionic and neutral particles. These are analyzed mined by the orbital energies EK, EL1, and EL2 of
by mass spectroscopic techniques, such as sec- the three orbitals involved. The Auger energy
ondary ion mass spectroscopy (SIMS), and EKLL is then given by:
secondary neutral mass spectroscopy (SNMS). EKLL ¼ EK EL1 EL3 dEF ð23Þ
Less frequently used is laser microprobe mass
analysis (LAMMA). Relevant information on where dE is a relaxation energy, and F the
the properties of the various surface analytical spectrometer work function. Clearly, EKLL is
techniques is summarized in Table 11. characteristic for an element and independent of
The physical principles of the various tech- the initial ionization process. Thus, both tech-
niques have been discussed in several articles niques permit the elemental constituents of a
and monographs [375,376]. surface to be identified.
The information depth of both electron spec-
Electron Spectroscopy (AES, XPS) (see troscopies is determined by the mean free path
also ! Surface and Thin-film Analysis – of the emitted electrons, which depends on the
Auger Electron Spectroscopy (AES)). These kinetic energy of the electron in the solid matrix.
techniques use electrons as information carriers. This dependence is known [375–377]. The elec-
The electrons can be produced by the absorption tron mean free path is typically larger in oxides
of photons resulting in photoemission. In XPS, than in metals at equal energy, and it is particu-
X-ray photons are used to ionize core levels, and larly large for zeolites because of their low
Table 11. Characteristics of surface analytical techniques in standard applications (adapted from ref. [375])
Information Technique
density. Together with reported ionization cross Secondary Particles Ion bombardment of
sections and, in the case of AES, Auger decay a surface leads to ion etching with the release of
probabilities, quantitative surface analysis is atoms and molecular fragments with varying
possible. The ratios of integral peak areas are charges (anions, cations, and neutrals) and exci-
proportional to concentration ratios. These can tation states. The mass analysis of secondary ions
be analyzed as a function of preparation and by mass spectrometry [secondary ion mass spec-
treatment conditions of a given catalyst system troscopy (SIMS)] has been developed as a highly
(e.g., supported metal, oxide, or sulfide cata- sensitive and powerful surface analytical method
lysts) and compared with model calcula- (! Surface and Thin-Film Analysis – Second-
tions [376]. Information on the elemental ary ion Mass Spectrometry) [382,383]. Although
distributions and on dispersions of active com- destructive because of the need for sputtering,
ponents thus becomes available. the sputtering rate can be kept low in the
so-called static mode (low primary-ion current
Ion-scattering Spectroscopies [375] (see density) so that the surface remains essentially
also ! Surface and Thin-Film Analysis). In unchanged. Since the sputtered particles are
ion-scattering spectroscopies solid surfaces are preferentially released from the first two atomic
bombarded with monoenergetic ions, which are layers, the SIMS technique is surface-sensitive.
scattered on the top atomic layer (ion energies of In contrast to the ion-scattering techniques, not
about 0.5 – 5 keV, low-energy ion scattering only atomic constituents of a surface can be
(LEIS) [378,379]) or within near-surface re- detected but information on the local environ-
gions (ion energies of about 0.1 – 23 MeV, ment of an atom in the surface can be obtained by
Rutherford backscattering (RBS) [380,381]). In analysis of molecular fragments. The detection
both cases the collision kinematics can be of light elements, particularly hydrogen, is also
described as simple binary collisions, so that possible. Quantification of the method is diffi-
the kinetic energy of the backscattered ion is cult, although not entirely impossible.
directly dependent on the ratio of the masses of A high percentage of the sputtered secondary
the projectile and the scattering target atom and particles are neutral and must be postionized for
on the scattering angle. The mass of the projec- mass spectroscopic analysis [secondary neutral
tile is known and the scattering angle is fixed mass spectroscopy (SNMS), ! Surface and
and determined by the geometry of the spec- Thin-Film Analysis – Secondary Natural Mass
trometer. Thus, the mass, and hence the identity, Spectrometry (SNMS)] [384,173]. Post-ioniza-
of the scattering target atoms can be determined tion can be achieved by electron impact in a
unequivocally. plasma or by an electron beam. Alternatively,
The LEIS technique provides information on resonant and nonresonant laser ionization can
the nature of the atomic constituents of the be applied. Applications of SNMS for catalyst
topmost atomic layers. Quantitative analysis, characterization have still not been reported.
however, is difficult since neutralization proba-
bility, which makes the technique surface sen-
sitive, is not easily available. Only a few percent 6.2.2. Valence States and Redox
of the primary ions are backscattered as ions in Properties
the case of noble gas ion (e.g., Heþ). The
technique can be applied for the characteriza- Electron Spectroscopies X-ray photoelec-
tion of real catalyst surfaces, although surface tron spectroscopy (XPS) and Auger electron
roughness reduces the signal intensity. spectroscopy (AES), in addition to elemental
In contrast, in the energy regime of RBS the analysis, permit information to be obtained on
scattering cross sections can be calculated ex- the valence and bonding states of a given ele-
actly. As a consequence, quantitative analysis is ment. This is due to the fact that the core-level
possible by RBS, but the surface sensitivity is binding energies and Auger kinetic energies are
lower than for LEIS. In optimal cases an infor- dependent on the chemical state, which leads to
mation depth of 1 – 5 nm can be achieved. A characteristic chemical shifts. In solids, the
combined application of LEIS, RBS, and Madelung potential also plays an important
perhaps XPS is often most informative [375]. role [376,385,386]. In addition, the ionization
60 Heterogeneous Catalysis and Solid Catalysts
solid). Typical systems that have been studied surfaces, and surface anion or cation radicals
by optical spectroscopy are transition metal and deliberately produced by organic molecules as
base metal oxides, transition metal ions or com- probes for the redox properties of the solid
plexes grafted on support surfaces, and transi- catalyst. Radical species (e.g., in connection
tion metal ion-exchanged zeolites. with coke formation) formed during catalytic
While spectra of liquid samples can be re- reactions have also been detected.
corded in the transmission mode, catalyst pow-
ders must be studied by the diffuse reflectance Thermal Analysis Thermoanalytical tech-
technique (DRS) [389,390,393]. The measured niques such as differential thermal analysis
diffuse reflectance can be converted into the so- (DTA), thermogravimetry (TG), and differential
called Schuster – Kubelka – Munk (SKM) scanning calorimetry (DSC) are well-estab-
function, which is directly proportional to the lished methods (! Thermal Analysis and
absorption coefficient. The wavelength depen- Calorimetry) in solid-state chemistry [398,399]
dence of the SKM function is thus equivalent to which have successfully been applied to inves-
an absorption spectrum, provided the scattering tigating the genesis of solid catalytic materials.
coefficient is independent of the wavelength. They can also be used to follow reduction and
This condition is often fulfilled in the UV and oxidation processes by measuring either ther-
VIS spectral regions. Simple quartz cells for in mal effects and/or weight changes. When com-
situ treatments can be designed, to which an bined with an on-line mass spectrometer,
EPR tube can also be connected for simulta- changes in the gas-phase composition occurring
neous optical spectroscopy and EPR on the during chemical transformations of the solid
same sample [388]. sample can be monitored simultaneously.
Luminescence spectroscopy [394,395] has In temperature-programmed reduction
proved to be a valuable addition to the spectros- (TPR), as first described by ROBERTSON et
copy techniques for characterization of solid al. [400], a stream of inert gas (N2 or Ar) contain-
catalysts under well-defined conditions. ing ca. 5 vol % H2 is passed through the catalyst
As mentioned above, electron paramagnetic bed of a flow reactor containing a reducible solid
resonance (EPR) is used to study paramagnetic catalyst [401]. By monitoring continuously the
species in catalytic materials. Besides the sim- H2 concentration in the gas stream and its even-
ple qualitative (and quantitative) detection of tual consumption with a thermal conductivity
the presence of paramagnetic sites, the spin detector while heating the sample with a linear
density distribution at the paramagnetic center temperature ramp of ca. 10 K/min, the rates of
and on the neighboring atoms can be deduced reduction are obtained as a function of time (or
from the spectra. Simulations of EPR spectra are temperature). The total amount of H2 consumed
often useful for full interpretation. The extreme- determines the reduction equivalents present in
ly high sensitivity of the EPR technique can the catalyst, and detailed analysis of the experi-
be an advantage but also a drawback because the ment permits the kinetic parameters of the re-
importance of minority radical species may be duction process to be determined and provides
overemphasized. EPR is not surface-sensitive. information on reduction mechanisms. Charac-
However, radical species in the surface can teristic numbers which depend on the experi-
easily be identified by exposing the sample to mental parameters (amount of reducible species
paramagnetic O2, which leads to significant present, H2 concentration, flow rate, and tem-
broadening or disappearance of signals of perature ramp) have been defined [328,329].
surface species because of dipole – dipole These numbers must be kept in certain ranges
interactions. for optimal performance of the experiment.
Several reviews on the use of EPR in TPR experiments have been used to investi-
catalyst characterization have been published gate the reduction behavior of bulk and
[388,396,397]. Typical applications of EPR are supported reducible species, solid solutions,
the detection of paramagnetic states of transi- promoted metal catalysts, metals in zeolites,
tion metal ions and analysis of the symmetry of and of supported sulfides and of nitrides [401].
their ligand sphere and/or their coordination, Temperature-programmed oxidation (TPO)
redox properties of catalytic materials and their is an equally valuable technique for investigat-
62 Heterogeneous Catalysis and Solid Catalysts
ing the oxidation kinetics and mechanisms of excitation of covalent surface alkoxy species.
reduced materials [401]. Cyclic application of Because of the proposed bifunctional nature of
TPR and TPO provides information on the active acid sites in heterogeneous acid catalysis,
redox behavior of catalytic materials, e.g., of it is necessary to characterize both the acidic and
catalysts for selective catalytic oxidations. basic properties of solid catalysts. Many differ-
ent methods have been developed for the char-
acterization of acidity, but only little is known
6.2.3. Acidity and Basicity about the basic character, particularly of mate-
rials that are typically considered to be acid
Acid-catalyzed reactions are among the indus- catalysts.
trially most important hydrocarbon conver-
sions. Acid sites can be classified as Lewis Chemical Characterization [405]. Titra-
acidic sites, such as coordinatively unsaturated tion methods in aqueous medium are not very
cations (e.g., Al3þ on the surface of partially informative, because H2O tends to strongly mod-
dehydroxylated alumina, and Brønsted acidic ify surface properties by molecular or dissocia-
sites, which are typically surface OH groups as, tive chemisorption. Therefore, nonaqueous
e.g., in H forms of zeolites. Carbenium and methods have been proposed, in which the sol-
carbonium ions are thought to be formed by vent (e.g., benzene or isooctane) does not or only
protonation of hydrocarbons on these groups. weakly interact with the catalyst surface. Ham-
Surface oxygen ions may function as Lewis mett indicators were used to determine the acid
basic centers, and if strong enough they may strength in terms of the Hammett – Deyrup H0
abstract protons from hydrocarbon molecules to function:
form carbanion intermediates. A typical solid H0 ¼ log aHþ ðfB =fBHþ Þ ð26Þ
base is MgO.
þ
For characterization of acid and base prop- where aþ H is the proton activity and fB and fBH
erties, the nature (Lewis or Brønsted) of the are the activity coefficients of the basic probe
sites, the acid or base strength, and the number and its protonated form, respectively. A series of
of sites per unit surface area of a solid catalyst Hammett indicators covers the range of 18 <
must be determined. Brønsted acidity is almost H0 < 4, where H0 ¼ 12 corresponds to 100 %
certainly required for all acid-catalyzed reac- H2SO4.
tions. However, the mechanistic details on sur- Site densities and acid strength distributions
faces are significantly different from the well- were determined by the n-butylamine titration
known carbenium and carbonium ion chemistry method [406]. As these titration and indicator
in solution, because of the lack of the stabilizing methods can yield erroneous results [407], they
effect of solvation in heterogeneously catalyzed are not frequently used today.
gas-phase reactions. As shown by KAZANS- Isosteric heats of adsorption of strong bases
KY [404], the electronic ground state of surface (e.g., pyridine) may be considered as measures
acidic OH groups of oxides and in H forms of of acid strength. However, a discrimination
zeolites is essentially covalent. The main differ- between Lewis and Brønsted sites is not
ences in their acid strength are thought to be due possible.
to the energetic positions of their electronically Temperature-programmed desorption [also
excited heterolytic terms. Similarly, the interac- called thermal desorption spectroscopy (TDS)]
tion of acid groups with alkenes does not result of basic probe molecules has been developed as
in the formation of adsorbed carbenium ions but a powerful tool for the characterization of solid
rather in the formation of more stable covalent acids [408,409]. In this method, a strong base is
alkoxides. Basic sites (surface O2 ions) in the isothermally pre-adsorbed on an acidic catalyst
vicinity of OH groups could be involved in this and then exposed to a stream of inert gas (e.g.,
process. Carbenium ions (and even more so He). Heating by a temperature ramp (ca. 10 K/
carbonium ions) are therefore not considered min) leads to desorption of the base. The inte-
to be reaction intermediates in solid acid catal- gral area of the desorption peak gives the total
ysis, but rather excited unstable ion pairs or acid site density, and the position of the peak
transition states resulting from electronic maximum provides the activation energy of
Heterogeneous Catalysis and Solid Catalysts 63
desorption (which may be close or identical to (Eq. 28) [421] and hence, of the acidity of the
the heat of adsorption), which can be considered OH group.
to be a measure of the acid strength. This
approach has been applied for investigations of jDnOH j1=2 DHB ð28Þ
H forms of zeolites using ammonia as the Simultaneously, internal molecular modes of
probe [410,411]. However, discrimination the base B are modified, particularly when
between Lewis and Brønsted acid sites is again protonation occurs. These changes can also be
only possible with the assistance of, e.g., used for the interpretation of the bonding type of
vibrational spectroscopy. the probe. Strong bases such as the traditional
probe molecules ammonia and pyridine are
Microcalorimetry [408]. Differential heats
protonated by even very weak Brønsted sites
of adsorption of probe molecules can be mea-
which may not be at all relevant in acid catalysis.
sured with high accuracy by heat-flow calorim-
Weaker bases such as nitriles, carbon monoxide,
etry and differential scanning calorimetry. These
and even dinitrogen and dihydrogen only un-
data provide information on the acid (or base)
dergo hydrogen bonding (hydrogen bonding
strength distribution. Ammonia and other
method [416]), but due to their weak interac-
amines have been used as probes for acid sites
tions they are very specific and can provide very
on oxides [412] and in H forms of zeo-
detailed information on the properties of acidic
lites [413,414], and carbon dioxide and sulfur
surfaces.
dioxide were adsorbed as acidic probes on sev-
The same bases can be used for the detection
eral oxides [412].
of Lewis acid sites L, with which they form
Vibrational spectroscopy [415,420]. surface coordination compounds:
Transmission infrared spectroscopy is the most LþB Ð L B ð29Þ
frequently applied technique for investigations
into acidic and basic properties of solid cata- The frequency shifts of the internal B modes
lysts. Surface hydroxyl groups can easily be are a measure of the nature and strength of the
detected since they function as dipolar oscilla- coordinative bond. For example, carbon mon-
tors. However, the stretching frequency of un- oxide when coordinated to L sites undergoes
perturbed OH groups can not be taken as a very typical shifts of the C – O stretching fre-
measure of the acid strength. Lewis acidic and quency which provide information on the nature
basic centers can only be detected by vibrational of the element and of the coordinative bond, on
frequencies with the adsorption of suitable the oxidation state, and on the coordination of
probe molecules. Criteria for the selection of the L site [415,420].
optimal probe molecules have been defined by The investigation of basic sites O2 by acidic
KNOEZINGER et al. [415,420]. probe molecules AH with analysis of the vibra-
The use of basic probe molecules permits a tional spectra is much less advanced than that of
discrimination between Brønsted and Lewis acid sites. The hydrogen-bond method can in
acid sites. When a base B is adsorbed on an principle be applied:
acidic OH group, hydrogen bonding followed
eventually by protonation of the base may occur O2 þHA Ð O2 HA ð30Þ
(Eq. 20): Here the shift of the H–A stretching mode is a
þ measure of the hydrogen-bond strength and
OHþB Ð OHB Ð O H B ð27Þ
hence, the basic character (proton affinity) of
The strength of the hydrogen bond and the the surface O2 site. Recently, CH compounds
ability of the OH group to protonate the base is such as trichloromethane [416], acetylene and
determined by the acid strength of the surface substituted acetylenes [420,422] and even meth-
OH group and by the base strength (or proton ane [423] were proposed and successfully tested
affinity) of B. When hydrogen bonding occurs, as acidic probe molecules. Pyrrole [419] and
the induced frequency shift of the O – H several Lewis acids [415] have also been used.
stretching mode Dn‘OH is a measure of the Surface chemical transformations of, e.g.,
strength of the hydrogen bond DHB CO2, alcohols, ketones, acetonitrile, and
64 Heterogeneous Catalysis and Solid Catalysts
pyridine gave detailed information on the bi- reached. Catalyst particles of irregular form are
functional acid – base pair character of several tested in a cylinder provided with a ram. After a
oxides, particularly of alumina [415,424]. definite pressure is applied, the sample is dis-
charged, and the weight percent of fines formed
Nuclear Magnetic Resonance [425,427]. during the test is determined by screening.
Solid-state 1 H magic-angle spinning (MAS) Tests for impact strength and resistance
NMR spectroscopy measures proton chemical against abrasion or attrition are carried out
shifts, which were thought to reflect the depro- under dynamic conditions. For impact testing
tonation energies of surface OH groups. How- of very strong catalysts (e.g., ammonia synthe-
ever, proton chemical shifts are also very sensi- sis catalysts), a mass of 500 – 1000 g is dropped
tive to hydrogen bonding. Therefore, changes in on the particle from a standard height and the
proton chemical shifts induced by hydrogen percentage of unbroken, split, and broken sam-
bonding of probe molecules can also be used ples out of 20 or more is recorded. Abrasion tests
for the characterization of protic acidity. on tableted and extruded catalysts are carried
Dissociative chemisorption of CH3I was pro- out in a rotating horizontal steel cylinder pro-
posed for characterization of surface basicity by vided with one baffle. The percent of fines
13
C NMR spectroscopy [428]. (based on the mass of the catalyst tested) formed
after 1 h is reported as attrition loss. The attrition
loss of fluid catalysts is measured by exposing
6.3. Mechanical Properties [429] the catalyst particles to a high-velocity air
stream in a glass pipe. The fines formed during
Catalyst particles are exposed to diverse me- the test (prevented from escaping by a filter) are
chanical strains during transportation, charging reported as attrition loss expressed as the per-
to the reactor, and operation. In fixed bed re- centage of the sample charged [431].
actors catalyst particles must withstand pressure
caused by the mass of the catalyst charge and
erosion by high-velocity gas streams. In fluid- 6.4. Characterization of Solid
ized- and moving-bed reactors, the particles Catalysts under Working Conditions
must resist attrition from rubbing against each
other and from colliding with the walls of the The best description of a catalytic mechanism is
reactor system. The technical performance of the corresponding catalytic cycle. As a first step,
catalysts depends on their mechanical strength a detailed product analysis is required to differ-
to maintain integrity for a reasonable time in entiate between a single clean reaction and
spite of these strains. systems undergoing parallel and/or consecutive
There are three types of methods for deter- reactions. The microkinetic approach, as out-
mining the strength of catalysts used under static lined in Section Kinetics of Heterogeneous
conditions [430]. For pellets and rings with no Catalytic Reactions, for the prediction of the
areas of distortion (preferably sized 1 cm or overall rate of a catalytic reaction taking into
larger), the crushed (or crush) strength is deter- account the surface chemistry of the catalyst and
mined by exerting pressure on the specimen the elementary reactions involved, is the most
placed between two horizontal plates of a hy- promising procedure to predict a mechanism.
draulic press. The upper plate moves down until However, the results of microkinetic analyses
the specimen is crushed, at which point the may not always be unequivocal, and discrimi-
pressure is recorded. The test is repeated for nation between different kinetic models may not
several particles, and the values are averaged. In be straightforward. Therefore, additional infor-
the knife-edge hardness test, the upper plate of mation is necessary to prove or disprove the
the press is replaced by a knife with a 0.3 mm sequence of elementary steps (catalytic cycle)
edge. A mass of 1 kg is applied to the knife and that represents the mechanism of a catalyzed
the percentage of broken samples is recorded. reaction at the molecular level.
The mass is then raised in increments of 1 kg, Quantum chemical calculations at various
and the test is repeated until 100 % of the levels of sophistication and computer modeling
particles are broken or until a mass of 10 kg is procedures now permit structures of adsorbed
Heterogeneous Catalysis and Solid Catalysts 65
intermediates and transition states to be behavior of the catalyst surface can be studied.
elucidated and reaction energy diagrams to be Steady-state kinetic and mechanistic informa-
computed (see Section Molecular Modeling in tion which can be obtained from SSITKA
Heterogeneous Catalysis). includes concentrations of different types of
adsorbed reaction intermediates, coverages,
surface lifetimes, site heterogeneity, activity
6.4.1. Temporal Analysis of Products distributions, and identification of possible
(TAP Reactor) mechanisms [433].
The use of isotopes can greatly aids the
Transient kinetics measurements can also pro- elucidation of catalytic mechanisms [438]. The
vide quantitative values of kinetic parameters most frequently used isotopes are 2 H, 13 C, 14 C,
and elucidate individual reaction steps and 18 O. Deuterium-exchange reactions with
[432,433]. Pulse reactors are one type of tran- organic reactants yield isotopic distribution pat-
sient reactors. A valuable laboratory pulse terns which are often specific enough to elimi-
reactor (transient operation) is the TAP reactor nate a number of conceivable mechanisms.
(TAP ¼ temporal analysis of products). Pulses When carried out in conjunction with structure
containing small amounts of reactants (1013 – variations, isotopic distribution patterns may be
1017 molecules per pulse) are injected into the effective in narrowing the range of possible
evacuated reactor containing the catalyst bed. mechanisms, even though such studies cannot
The reactant/product molecules leaving the give “the mechanism” [34]. Deuterium labeling
reactor (response signal) are analyzed by mass is also used to determine which carbon atoms
spectroscopy with a time resolution of less than end up where or whether a reaction is inter- or
100 ms. This approach permits surface pro- intramolecular [34]. 13 C labeling can be used for
cesses on solid catalysts such as adsorption, the same purpose. Although nonradioactive
reaction, and desorption to be studied, and labels are preferred, radioactive tracers such as
14
reaction mechanisms and kinetic models to be C have also been used [439]. 18 O labeling has
established [434,436]. been applied to elucidate the relative rates of CO
In another kind of transient experiment, step and CO2 in methanol synthesis [440].
changes in concentrations are effected, and the Kinetic isotope effects [441,442] are due to
response of product concentration is measured the different masses of a given element and its
as a function of time. The analysis of this corresponding isotope. The resulting difference
response provides details of the course of in zero-point energy may lead to an increase in
reaction and permits kinetic parameters to be activation energy of the labeled molecule and
determined. therefore a reduction of the rate. Whether a
kinetic isotope effect occurs or not when an
atom in a certain position or group is isotopi-
6.4.2. Use of Isotopes cally labeled (i.e., an XH bond is replaced by
XD) for a catalytic reaction of interest
A powerful technique for the kinetic and mech- provides information on whether weakening or
anistic study of heterogeneous catalytic reac- rupture of the XH bond is involved in a
tions is steady-state isotopic-transient kinetic kinetically significant elementary step.
analysis (SSITKA) [433,437]. The technique is
based on the detection of isotopic labels in the
reactor effluent species versus time following a 6.4.3. Use of Substituents, Selective
step change in the isotopic labeling of one of the Feeding, and Poisoning
reactants in the reactor feed. Reactant and
product concentrations and flow rates remain Modification of organic molecules with suit-
undisturbed during the step change and — in able substituent groups may provide valuable
the absence of isotopic mass effects — steady- information on reaction mechanisms from the
state conditions are maintained under isotopic- stereochemistry of the reaction of inter-
transient operation. In contrast to other est [34,443,13]. Substituents generally also
transient experiments, the steady-state kinetic have electronic effects on the reactivity of a
66 Heterogeneous Catalysis and Solid Catalysts
parent reactant (substituent effects). Resulting Useful data arise from the experimental reso-
linear free-energy relationships for a series of lution of local velocity profiles by laser
substituents also assist the determination of Doppler anemometry/velocimetry (LDA, LDV)
kinetically significant reaction steps of a con- [447,449] and of spatial and temporal species
ceivable reaction mechanism [444,445,14,18], profiles by in situ, noninvasive methods such as
since the substituents directly affect the rela- Raman and laser-induced fluorescence (LIF)
tive energy of the transition state and hence the spectroscopy. For instance, an optically accessi-
activation barrier of a kinetically significant ble catalytic channel reactor can be used to
step. evaluate models for heterogeneous and homo-
Modification of molecules by substituents geneous chemistry as well as transport by the
may also cause intra- or intermolecular steric simultaneous detection of stable species by Ra-
effects [34], and steric interactions between man measurements and OH radicals by planar
adsorbate and catalyst surface can be studied. laser-induced fluorescence (PLIF) [450,451].
The latter studies provide almost the only way to For example, the onset of homogeneous ignition
directly probe the steric nature of active catalyt- of methane oxidation in a platinum-coated cata-
ic sites without confusion with adsorption sites lytic channel can be monitored by means of the
that are not catalytic sites [34]. distribution of OH radicals. While catalytic oxi-
Selective feeding and scavenging have been dation of methane along the channel walls re-
proposed for the characterization of reaction leases some OH radicals, at a certain point in the
intermediates [34]. Suppose Q is a suspected reactor a transition to homogeneous oxidation
intermediate for a particular reaction. This occurs accompanied by high concentrations of
hypothesis can be tested by adding (feeding) OH radicals in the flame region. Since transient
a compound to the reaction feed which is sup- phenomena such as ignition, extinction, and
posedly adsorbed to form the suspected inter- oscillations of reactions are very sensitive to
mediate Q, and by testing whether the added transport and kinetics, they can serve as mea-
compound is indeed converted to the expected sures for critical evaluation of theoretical mod-
product. In scavenging, a compound is added els. For instance, the reliability of different
which should react with the intermediate Q to heterogeneous and homogeneous reaction
form another compound which is not normally a schemes proposed in the literature was investi-
product. gated by comparison of the experimentally
The nature of catalytic sites can be tested and derived ignition distances with numerical
their density estimated by selective poisoning elliptic two-dimensional simulations of the flow
[446]. field by using combinations of a variety of
schemes [452,453].
Analysis of the temperature and concentration Any spectroscopic technique which is surface-
profiles in the fluid phase over a working catalyst sensitive, has sufficiently high sensitivity, and
often provides valuable information on the func- can be applied under catalytic working condi-
tional behavior of the catalyst. Since, at high tions can provide valuable information on the
temperatures, conversion of reactants can also nature of sufficiently long lived intermediates.
proceed via homogeneous reactions in the fluid However, spectroscopy often detects spectator
phase aside from catalytic conversion, interac- species rather than reaction intermediates.
tion of homogeneous and heterogeneous chemi- Therefore, it is mandatory to demonstrate that
cal reactions and mass and heat transfer in the true intermediates are in fact seen. This can be
catalyst-containing reactor becomes important done by varying critical reaction parameters and
to fully understand the function of the catalyst. In monitoring the response of spectroscopic signal
particular in these cases, temporally and spatial- intensities as a function of time. Sufficiently
ly resolved profiles provide a more stringent test high temporal resolution of the applied spectro-
for model development and evaluation. scopic technique is therefore required.
Heterogeneous Catalysis and Solid Catalysts 67
7. Design and Technical Operation tivity of the catalyst, conditions have been
of Solid Catalysts delineated under which their adverse effects
can be minimized [89,455,456]. By carefully
7.1. Design Criteria for Solid matching operating conditions, catalyst, and
Catalysts [454] reactor, optimum catalyst performance can be
ensured.
Solid catalysts are used in a surprising variety Mass and heat transfer in heterogeneous
of shapes including powders and irregularly catalytic reactions occur in two ways. External
shaped particles, regular particles such as transport to the external surface involves diffu-
spheres and cylinders, and more complex ge- sion through the more or less stationary hydro-
ometries like monolithic honeycombs, gauzes, dynamic boundary layer that surrounds the cat-
and fibers. The most suitable geometry must be alyst particle. The thickness of this layer de-
carefully selected and adjusted according to the pends on the characteristics of the fluid and its
properties of the catalytically active material flow rate past the particle, and affects the rate of
and specific requirements of the chemical reac- mass and heat transfer. Internal transport to the
tion and catalytic reactor. Only rarely is the stationary fluid in the pores of catalyst particle is
catalytic reaction so fast that the outer geometric controlled by diffusion alone.
surface area of a nonporous catalytic body is Depending on the relative rates of the trans-
sufficiently large. Hence, porous catalysts are port processes and the catalytic reaction, three
mainly used in which the catalytically active or four types of regimes can be distinguished. In
surface area inside the structure often exceeds the kinetic regime the rates of external and
the geometric surface area by several orders of internal mass transport are much higher than
magnitude. In these cases, the pore structure the rate of the chemical reaction. Therefore,
must be accessible to the reactants while pro- concentration and temperature gradients
ducts are allowed to leave. Design criteria for between the fluid and the center of a catalyst
solid catalysts comprise the choice of appropri- particle are negligible, and the catalyst is fully
ate geometries with respect to highest possible utilized.
catalyst utilization and product selectivity in a In the internal diffusion regime, mass trans-
given reactor. These goals should be achieved at port in the catalyst pores is about as fast as, or
the lowest possible pressure drop over the slower than, the chemical reaction. In this case
reactor. there are considerable concentration gradients
along the length of the pores, the effectiveness
Diffusion, Mass- and Heat-Transfer Effects of the catalyst is impaired, and the apparent
[89,455,456]. Heterogeneous catalytic re- energy of activation is lower than that observed
actions take place on the external and internal in the kinetic regime.
surfaces (pores) of the catalyst. External and At an even lower ratio of rates of transport
internal concentration and temperature gradi- and conversion, there is an intermediate regime
ents can build up in the fluid (gas or liquid) in which the reaction takes place only on the
boundary layer around the catalyst particles and external surface of the catalyst particles while
inside the pores if mass and heat transfer be- the internal surface area in the pores is inactive.
tween the bulk of the fluid and the active sur- Because of the limited heat transfer in this
faces are not sufficiently fast. Such gradients regime, exothermic reactions can overheat the
tend to exist (1) in fixed-bed reactors charged catalyst, and this results in a higher activity than
with large, porous catalysts; (2) during opera- that corresponding to the temperature of the
tion at low mass flow velocities (mass flow rate fluid.
per unit cross-sectional area); or (3) in the case Finally, on further decreasing the ratio of the
of highly exothermic reactions. On the other rates of transport and conversion (e.g., by rais-
hand, gradient effects usually are absent when ing the temperature of the fluid), the external
small catalyst particles are used in fluidized-bed mass transfer regime is reached in which the
reactors. reaction rate is controlled by mass transfer, and
Because such internal and external gradients the concentration of the reactants at the surface
can substantially reduce the activity and selec- of the catalyst particles drops. Raising the
68 Heterogeneous Catalysis and Solid Catalysts
connected by macropores (> 50 nm) to the tions). The catalyst must not necessarily be kept
external surface area of the catalyst particle. in a packed bed but can be suspended in the
The micropores provide the needed high active liquid or gaseous fluid reactant mixture. In the
surface area, whereas the macropores facilitate fluidized-bed mode, the solid catalyst consist-
mass transport to and from the micropores. Such ing of fine powder (particle diameter 10 –
catalysts are especially suitable for operation at 200 mm) is kept in motion by an upward gas
process pressures below 3 MPa. At these pres- flow (fluidized-bed reactor, see Section Indus-
sures mass transport into pores smaller than trial Reactors). If the fluid is a liquid the catalyst
100 – 1000 nm occurs increasingly through can be suspended easily in a CSTR by efficient
Knudsen diffusion involving molecular colli- stirring (slurry reactor, see Section Industrial
sions with the pore wall rather than between Reactors). In so-called riser reactors, catalyst
molecules [89,456]. material is continuously introduced into and
In fast processes occurring in the regime of removed from the reactor with the reactant and
external mass transfer, the overall conversion product feeds.
rate is independent of the porosity of the catalyst Batch and semi-batch reactors operate under
and is essentially proportional to its external transient conditions. Discontinuous step or
surface area [463]. Examples of such reactions pulse operation necessarily results in transient
are oxidation of ammonia to nitric acid and conditions.
ammoxidation of methane to hydrogen cyanide Several catalytic reactor types are schemati-
carried out at 1070 – 1270 K on stacks of fine- cally shown in Figure 22. Tubular fixed bed
mesh Pt – Rh gauze. reactors (A) have an inlet flow n0 and an outlet
flow n of the reactant-product mixture.
The adiabatic fixed-bed reactor is shown in
7.2. Catalytic Reactors [469–473] Figure 22 B. Multitube fixed-bed reactors (C)
are used for highly exothermic reactions such as
7.2.1. Classification of Reactors the oxidation of o-xylene to phthalic anhydride.
[167,469,471] The principle of a CSTR is demonstrated as D. A
fluidized-bed reactor with catalyst recirculation
Catalytic reactors can be classified by their is sketched in E. A slurry CSTR reactor is
mode of operation under steady-state or tran- schematically shown in F. An alternative for
sient conditions or on their mode of contacting/ three-phase reactions (gas – liquid – solid) is
mixing of reactants and solid catalyst. the packed bubble column or slurry reactor (G).
Typical steady-state reactors are packed-bed Discontinuous batch reactors with internal and
tubular reactors under continuous flow condi- external recycling operating under transient
tions, either plug flow or mixed flow. In an ideal conditions are depicted as H and I, respectively.
tubular reactor ideal mixing takes place in the
radial direction, but there is no mixing in the
axial direction. Plug flow is attained in this case. 7.2.2. Laboratory Reactors [469,470]
Plug flow reactors can be operated either in
integral or differential mode. In the latter case, A compilation of laboratory reactors and their
single-pass experiments in small-scale reactors operation mode is given in Figure 23.
provide the data for differential conditions re- Laboratory reactors are small-scale reactors.
quired for analysis of the reaction kinetics. As Steady-state fixed-bed tubular flow reactors are
an alternative, the effluent from the differential- most frequently used for catalyst testing and
ly operating reactor can also be recycled exter- determination of the reaction kinetics on the
nally or internally, thus approaching a well- laboratory scale. These reactors are favored
mixed reactor system, the continuous-flow stir- because of the small amounts of catalyst re-
red tank reactor (CSTR). Without inlet and quired, the ease of operation, and the low cost.
outlet feed a continuous recycle flow results, Stirred tank reactors (e.g., with fixed or rotating
characteristic of a batch reactor in which the basket) and batch suspension reactors are less
feed composition changes with time (transient frequently used. Provided that heat- and mass-
conditions as opposed to steady-state condi- transfer limitations can be neglected under the
Heterogeneous Catalysis and Solid Catalysts 71
reactor inlet (mol s1). The ratio W/Fio is the in various ways. Randomly packed beds (deep
space – time. beds) require catalyst particles having different
Ancillary techniques in laboratory units for shapes such as spheres, cylinders, rings, flat disk
catalyst testing such as generation of feed pellets, or crushed material of a defined sieve
streams and product sampling are discussed fraction. The geometries and dimensions of the
in [474]. catalyst particles are dictated by pressure drop
The TAP reactor, a laboratory pulse reactor, and heat- and mass-transfer considerations. The
is described in Section Temporal Analysis of use of monolithic catalysts significantly reduces
Products (TAP Reactor). the pressure drop across the catalyst bed. This
type of catalyst is employed for example for
automobile exhaust gas purification and for the
7.2.3. Industrial Reactors [167,471] removal of nitrogen oxides from tail gases of
power stations.
Various types of industrial reactors and their Fixed-bed reactors can be operated under
operation mode are listed in Figure 24. adiabatic or nonadiabatic conditions. Adiabatic
reactors can be applied for reactions with low
Catalytic Fixed-Bed Reactors [475,477] heats of reaction such as gas purification. They
In the chemical industry fixed-bed reactors are consist of a cylindrical tube in which the catalyst
the standard type of reactors for heterogeneous- is packed on a screen and is traversed in axial
ly catalyzed gas-phase reactions (two-phase direction (Fig. 22 B). This design is particularly
reactors). Fixed catalyst beds can be realized suitable when short residence times and high
Heterogeneous Catalysis and Solid Catalysts 73
temperatures are required. In this case a fixed Nonadiabatic operation can be achieved with
bed of large diameter and small height (5 – fixed-bed reactors which are cooled or heated
20 mm) is used (shallow bed). As an example, through the reactor walls. Efficient heat ex-
for ammonia oxidation in nitric acid plants the change results in so-called isothermal reactors.
fixed bed consists of several layers of platinum A typical example is the multitubular reactor
wire gauze with bed diameters up to several schematically shown in Fig. 22 C, which is
meters. This type of reactor is limited to small used for highly exothermic and temperature
catalyst volumes. The radial flow concept is sensitive reactions (e.g., o-xylene oxidation)
preferred when large amounts of catalyst are with, e.g., salt melts as heat-transfer media. In
required [475]. In this reactor type, the catalyst a multitube reactor, the pressure drop must be
is charged in the annular space around an axially the same in each tube so that the gas flow is
located tube. The reactants are traversing radi- distributed uniformly over the tubes. Small
ally, either from the inside or from the outside of changes in the packing density in the tubes can
perforated plate rings. Because of the low pres- cause uneven heat transfer and, in the case of
sure drop, smaller catalyst pellets (4 4 or highly exothermic reactions, hot spots and se-
3 3 mm) can be used in this reactor type. lectivity loss. For these reasons multitube re-
Only limited conversions can be achieved by actors are filled by special equipment that
adiabatic reactors because of the necessary con- charges each tube with the same amount of
trol of the adiabatic temperature change. Multi- catalyst at a definite rate. After filling, the tubes
stage reactors consisting of several sequential are checked for pressure drop, and if necessary,
adiabatic stages which are separated by inter- the charge is adjusted.
stage heat exchangers have therefore been Autothermal reactors can favorably be ap-
introduced. plied for exothermic and temperature sensitive
74 Heterogeneous Catalysis and Solid Catalysts
*
Undesired bypass of reactants due to bubble
development
*
Catalyst attrition
*
Erosion of internals resulting from high
solids velocities
*
phase component (which is to be dissolved in a Selective removal of catalytic poison in the
liquid-phase component) and a finely dis- entrance zone of the bed
*
persed solid catalyst (three-phase reactors). Simple catalyst regeneration
The particle size of the solid catalyst is kept
sufficiently small (< 200 mm) that it remains Drawbacks of trickle-bed reactors are:
suspended by the turbulence of the liquid in the
slurry reactor. This is in contrast to three-phase Poor heat transfer
fluidized-bed reactors, in which an upward Partial utilization of the catalyst in case of the
liquid flow is required to suspend the larger incomplete wetting
catalyst particles. Possibility of “brooks” formation
On the basis of the contacting pattern of the
phases and the mechanical devices that achieve The successful performance of the trickle-
contact and the mass transfer, nine types of phase reactors depends on the suitable diameter/
slurry reactors can be distinguished [483]: length ratio, catalyst shape and size, and the
liquid flow distribution through the catalyst bed.
1. Slurry bubble column The catalyst particle size is limited by the
2. Countercurrent column allowed pressure drop. Larger sizes (6 – 10 mm
3. Cocurrent upflow diameter) are therefore preferred, which,
4. Cocurrent downflow however, can bring diffusion problems.
5. Stirred vessel The “bubble-flow” version is favored in par-
6. Draft-tube reactor ticular for reactions with a low space velocity.
7. Tray column A good heat transfer and no problems with
8. Rotating-disk or multiagitator column an incomplete catalyst wetting are the main
9. Three-phase spray column advantages of the “bubble-flow” reactors.
Both types of the three-phase reactors
Slurry reactors are industrially applied for a have found numerous industrial applications,
multitude of processes [484], many of which are e.g.:
heterogeneously catalyzed processes for hydro-
*
genation of edible oils. A new development is Hydrotreating of petroleum fractions at
the continuous Fischer – Tropsch slurry synthe- 570 – 620 K, 30 – 60 bar on Ni–MoO3–
sis process of SASOL in South Africa [485]. Al2O3 catalysts.
*
Three-phase reactors are classified as fixed- Hydrocracking of high boiling distillates at
bed or suspension reactors depending on the 570 – 670 K, 200 – 220 bar on Ni–MoO3–
catalyst arrangement and shape: Y–zeolite–alumina catalysts.
*
Fixed-bed reactors operate either in the trick- Selective hydogenation of C4-fractions (re-
le-bed or in the bubble-flow mode [483]. In the moval of dienes and alkines) at 300 –
first case, liquid reactants or reactants dissolved 325 K, 5 – 20 bar on Pd-Al2O3 catalysts.
*
in a solvent are flowing downward through the Hydrogenation of aliphatic carbonyl com-
catalyst bed and the gaseous reactants are con- pounds to alcohols at 370 – 420 K, 30 bar
ducted in the countercurrent or concurrent on CuO–Cr2O3 catalysts.
direction.
In the bubble-flow reactors, liquid and gas- Suspension reactors [483,484] are operated
eous reactants are fed into the bottom of the successfully in the chemical industry because of
column and are flowing upward through the their good heat transfer, temperature control,
catalyst fixed-bed. catalyst utilization, and simple design. Because
The trickle-bed arrangement has some ad- of the small catalyst particle size, there are no
vantages such as: problems with internal diffusion. Suspension
reactors operate either in the discontinuous or
*
Fast diffusion of gases through the liquid in the continuous mode. One serious disadvan-
film to the catalyst surface tage is the difficult catalyst separation, especial-
*
Lower back-mixing ly if fine particles have to be removed from the
*
No problems with catalyst separation viscous liquid.
Heterogeneous Catalysis and Solid Catalysts 77
Currently two types of suspension reactors series of interconnecting channels having dia-
are in use: stirred vessels and three-phase bubble meters between 10 and 1000 mm that are
columns. formed in a planar surface in which small
In the case of stirred vessels the catalyst quantities of reagents are manipulated (see also
particles (mainly smaller than 200 mm) are ! Microreactors – Modeling and Simulation).
suspended in the liquid reactant or solutions of Among the advantages of microstructured re-
reactants, whereas gaseous reactants are intro- actors over conventional catalytic reactors are
duced at the bottom of the vessel through per- high heat-transfer coefficients, increased sur-
forated tubes, plates or nozzles. The vessels are face-to-volume ratios of up to 50 000 m2 m3,
equipped with different types of stirrers or as opposed to 1000 m2 m3 for conventional
turbines keeping the catalyst suspended. Cool- catalytic laboratory reactors, shorter mixing
ing and heating coils as well as the gas recycle times, and localized control of concentration
system belong to the standard equipment. Stir- gradients. The small scales reduce exposure to
red vessels operate mostly discontinuously. toxic or hazardous materials, and the enclosed
However, if continuous operation is favored, nature of the microstructured reactors permits
then stirred vessels are arranged in a cascade greater ease of containment in the event of a
to complete the required conversion. runaway reaction. Furthermore, the highly ef-
Bubble columns are mainly continuously ficient heat transfer as well as high surface
operating three-phase reactors. The gas is intro- areas available for adsorption of radicals allow
duced at the bottom of the column through reactions to be carried out beyond the explo-
nozzles, perforated plates or tubes. In the stan- sion limit [488,492,493].
dard arrangement the liquid reactant flows in the Despite their small size, microstructured re-
cocurrent direction with the gas. In some cases actors can be used for synthetic chemistry [494],
stirrers are installed to keep powdered catalysts since as few as 1000 microchannels operating
in the suspension. continuously could produce 1 kg of product per
The gaseous reactants can be recycled by an day. While several types of laboratory-scale
external loop or by an internal system, such as a microstructured reactors are already commer-
Venturi jet tube. This equipment is driven by a cially available, further developments are still
recycle of the slurry using a simple pump. The required to make microstructured reactors ma-
Venturi tube is sucking the gas from the free board ture for industrial application. One of the most
above the reactor back into the slurry. Heat ex- advanced designs targeted at large-scale appli-
changers can be installed in the loop in both cases. cations for exothermic gas-phase reactions is
The main advantages of bubble columns are the DEMiS project of Degussa and Uhde [495].
simple and low-priced construction, good heat The state of development of microstructured
transfer, and good temperature control. reactors for heterogeneously catalyzed gas-
Suspension reactors are used predominant- phase and liquid-phase reactions has been sum-
ly for fat and oil hydrogenation 420 – 470 K, at marized [319]. Coating of wall materials with
5 – 15 bar using various Ni–kieselguhr catalysts. catalysts, strategies for replacement of spent
Also, hydrogenolysis of fatty acid methyl catalysts, and the reduction of overall apparatus
esters to fatty alcohols is performed in suspen- size appear to be the most challenging obstacles
sion reactors at 450 – 490 K, 200 – 300 bar on to be overcome. It is also evident that in many
promoted copper chromites (CuO–Cr2O3). cases more active catalysts are required for full
Further applications are: syntheses of acetal- utilization of microstructured reactors.
dehyde and of vinyl acetate according to the
Wacker process. Unsteady-State Reactor Operation [496]
Forced unsteady-state reactor operation has
been applied to continuous catalytic processes
7.2.4. Special Reactor Types in fixed and f1uidized-bed reactors. This oper-
and Processes ating mode can lead to improved reactor
performance. Nonlinearity of chemical reac-
Microstructured Reactors [486–491] A tion rates and complexity of reaction systems
microstructured reactor can be defined as a are responsible for conversion or selectivity
78 Heterogeneous Catalysis and Solid Catalysts
performed simultaneously, e.g., for a reaction of 7. Better heat transfer than in gases
the type 8. Use of clustering to alter selectivities
the commercially widespread multipurpose CFD only loss of activity but also a decrease in
software packages such as FLUENT [512], selectivity is usually caused by catalyst deacti-
STAR-CD [513], FIRE [514], CFD-ACEþ [515], vation [529–531].
and CFX [516], a variety of multipurpose and The activity loss can be compensated within
specialized CFD codes have been developed certain limits by increasing the reaction temper-
in academia and at research facilities such as ature. However, if such compensation is not
MP-SALSA [517]. efficient enough, the catalyst must be regener-
From a reaction-engineering perspective, ated or replaced.
computational fluid dynamics simulations have The main reasons for catalyst deactivation
matured to a powerful tool for understanding are:
mass and heat transport in catalytic reactors.
Initially, CFD calculations focused on a better 1. Poisoning
understanding of mixing, mass transfer to en- 2. Fouling
hance reaction rates, diffusion in porous media, 3. Thermal degradation
and heat transfer. Later, the flow field and heat 4. Volatilization of active components
transport models were also coupled with models
for heterogeneous chemical reactions. So far, Some types of catalyst deactivation are re-
most of these models are based on the mean- versible, e.g., catalyst fouling and some special
field approximation as discussed in Section types of poisoning. Other types of deactivation
Mean-Field Approximation, in which the local are mostly irreversible [529,530,532].
state of the surface is described by its coverage
with adsorbed species averaged on a microscop- Catalyst Poisoning The blocking of active
ic scale. sites by certain elements or compounds accom-
Detailed CFD simulations of catalytic reac- panied by chemisorption or formation of surface
tors, often including multistep reaction mec- complexes are the main causes of catalyst de-
hanisms, have been carried out for catalytic activation [529,530,532]. If the chemisorption
channel reactors with laminar [518] and tur- is weak, reactivation may occur; if it is strong,
bulent [519] flow fields, monolithic reac- deactivation results. Chemical species often
tors [520–524], fixed-bed reactors [525,526], considered as poisons can be divided in five
wire-gauze reactors [527,528], reactors with classes:
multiphase flow [512], and others. CFD simula-
tions are becoming a powerful tool for under- 1. Group 15 and 16 elements such as As, P, S,
standing the behavior of catalytic reactors and Se, and Te
in supporting the design and optimization of 2. Metals and ions, e.g., Pb, Hg, Sb, Cd
reactors and processes. 3. Molecules with free electron pairs that are
strongly chemisorbed, e.g., CO, HCN, NO
4. NH3, H2O and organic bases, e.g., aliphatic
or aromatic amines, pyridine, and quinoline
7.3. Catalyst Deactivation 5. Various compounds which can react with dif-
and Regeneration ferent active sites, e.g., NO, SO2, SO3, CO2.
7.3.1. Different Types of Deactivation Elements of class 1 and their compounds, for
example, H2S, mercaptans, PH3, and AsH3, are
As has been observed in the laboratory and in very strong poisons for metallic catalysts, espe-
industrial application, heterogeneous catalysts cially for those containing Ni, Co, Cu, Fe, and
are deactivated during time on stream. For noble metals [529,530,532].
example, in fluid-bed catalytic cracking and Elements of the class 2 can form alloys with
propene ammoxidation the catalyst life is limit- active metals and deactivate various systems in
ed to a few seconds or minutes, while in other this way [529,533].
reactions, such as NH3 and CO oxidation the CO is chemisorbed strongly on Ni or Co and
catalyst remains active for several years. Not blocks active sites. Below 450 K and at elevated
Heterogeneous Catalysis and Solid Catalysts 81
pressure the formation of volatile metal carbo- is the reduction of the surface area of alumina
nyls is possible [529,530], and catalyst activity from 250 m2 g1 (g phase) to 1 – 2 m2 g1
is strongly reduced. (a phase) by thermal treatment between 870
Ammonia, amines, alcohols, and water are and 1270 K.
well known poisons for acidic catalysts, espe- Alternating oxidation and reduction of the
cially for those based on zeolites [529,534]. system, as well as temperature fluctuations, are
Catalysts or carriers containing alkali metals often accompanied by activity losses and can
are sensitive to CO2, SO2, and SO3. cause mechanical strain in catalyst pellets.
Therefore, mechanical strength of catalyst par-
Catalyst Fouling Because most catalysts ticles has major industrial importance.
and supports are porous, blockage of pores,
especially of micropores, by polymeric com- Volatization of Active Components Some
pounds is a frequent cause of catalyst deactiva- catalytic systems containing P2O5, MoO3, Bi2O3,
tion. At elevated temperatures (> 770 K) such etc. lose their activity on heating close to the
polymers are transformed to black carbona- sublimation point. Cu, Ni, Fe and noble metals
ceous materials generally called coke [529,535]. can escape from catalysts after conversion to
Catalysts possessing acidic or hydrogenating – volatile chlorides if traces of chlorine are present
dehydrogenating functions are especially sensi- in the feed.
tive to coking.
There are different types of coke, such as Ca,
Cb, carbidic or graphitic coke, and whisker 7.3.2. Catalyst Regeneration
carbon [529]. Ca is atomic carbon formed as
a result of hydrocarbon cracking on nickel The regeneration of metallic catalysts poisoned
surfaces above 870 K. Ca carbon can be trans- by Group 16 elements is generally rather diffi-
formed at higher temperatures to polymeric cult. For example, oxidation of sulfur-poisoned
carbon (Cb) which has a strongly deactivating metallic catalysts converts metal sulfides to
effect. Ca carbon can also dissolve in metals and SO3, which desorbs from metals. However, if
forms metal carbides, and it may precipitate at the catalyst or carrier contains Al2O3, ZnO,
grain boundaries. Metal-dissolved carbon may MgO then SO3 forms the corresponding sul-
also initiate the growth of carbon whiskers, fates. When the catalyst is subsequently brought
which can bear metal particles at their tops. on-line under reducing conditions, then H2S is
Coke formation can be minimized, for ex- formed from sulfates and the catalyst will be
ample, in methane steam reforming by suffi- repoisoned [529,537].
ciently high steam/methane ratio or/and by the Therefore it is necessary to remove poisons
alkalization of the carrier. from the feed as completely as possible. Further
prevention is the installation of a guard-bed
Thermal Degradation One type of ther- containing effective poison adsorbents in front
mal degradation is the agglomeration of small of the reactor.
metal crystallites below the melting point, Ni catalysts poisoned with CO or HCN can
called sintering [529]. The rate of sintering be regenerated by H2 treatment at temperatures
increases with increasing temperature. The that allow formation of methane and NH3,
presence of steam in the feed can accelerate the respectively.
sintering of metal crystallites. The original activity of acidic catalysts poi-
Another type of thermal degradation are sol- soned partially by H2O, alcohols, NH3, and
id-solid reactions occurring especially at higher amines can be restored by thermal treatment at
temperatures (above 970 K). Examples are re- sufficiently high temperatures.
actions between metals, such as Cu, Ni, Co, and From the industrial point of view, the regen-
alumina carriers which result in the formation of eration of coked catalysts is very important. The
inactive metal aluminates [529,536]. removal of coke depends on its structure and on
Also, phase changes belong to the category the catalyst composition. Alkali metals, espe-
of thermal degradations. A prominent example cially potassium, accelerate coke gasification.
82 Heterogeneous Catalysis and Solid Catalysts
A survey on steam reforming is given in [542]. using noble metal catalysts have been shown to
Nickel is the preferred catalyst but other group provide high syngas yields when operated at
8 – 10 metals are active as well, in particular Co high temperatures and millisecond contact
and Fe [543]. The expensive metals Pt, Ru, and times [547,552–554].
Rh show even higher activities [544]. A variety WGS is the most important step in the indus-
of industrial catalysts are available, most of trial production of hydrogen, ammonia, and
which are based on Ni/alumina with alkali metal other bulk chemicals utilizing syngas in respect
promoters, produced in the shape of pellets with to the adjustment of the CO/H2 ratio [540,555].
large external diameter and high void fraction Depending on the required CO conversion the
(rings, cylinders with holes, or ceramic foams), reaction is carried out in several stages. The first
and used in tubular reformers [542]. Present high-temperature shift (HTS) is carried out over
developments focus on compact reformers, effi- FeCr catalysts at temperatures between 280 and
cient coupling with heat exchangers, and heat 350 C. Since the equilibrium at high tempera-
recovery from the reformed gas. ture is unfavorable for complete conversion, a
An alternative technology for syngas gener- second stage, the low-temperature shift (LTS,
ation is exothermic catalytic partial oxidation 180 – 260 C), is added, in which CuZn- or
(CPOX) of hydrocarbons to syngas over metal CuZnAl-based catalysts are used to give a CO
catalysts, in particular Rh. The fuel (natural gas, content of 0.05 – 0.5 vol %. The produced CO2
vaporized liquid hydrocarbons, alcohols), pre- can be removed by scrubbing. Complete CO
mixed with oxygen at an atomic C/O ratio of 1 is removal, e.g., as needed for ammonia synthesis,
fed into a catalytic bed or monolith, in which the can be achieved by subsequent methanation
fuel is almost completely converted to synthesis over Ni catalysts. Since sulfur-containing com-
gas within few milliseconds at ca. 1000 C pounds such as H2S and carbonyl sulfide (COS)
(high-temperature catalysis) [545-547]. The are not removed, separate catalytic treatment is
largest hurdle for widespread application of usually necessary, e.g., hydrolysis of COS to
CPOX seems to be safety issues; therefore, H2S or oxidation with SO2 (Claus COS conver-
membrane [548] and microreactor [549] con- sion) and sour gas shift over Mo catalysts [556].
cepts are under development. The production of syngas and subsequent
Autothermal reforming is a combination of hydrogen is currently also of interest in the area
SR and POX, in which the heat for the reforming of energy-related catalysis such as fuel cells.
reaction is supplied by internal combustion of While for stationary applications natural gas is
the fuel with oxygen. Actually, CPOX can also the major fuel option, logistic fuels are consid-
be considered to be a two-stage process, in ered as potential feed in mobile applications, for
which the oxygen is first used to burn some of instance, to provide electricity by an auxiliary
the fuel and consecutive steam reforming of the power unit in a vehicle. Logistic fuels can, for
major part of the fuel produces the desired instance, efficiently be converted to syngas in
syngas [524]. ATR has already been widely compact on-board CPOX reactors; the syngas is
used in chemical industry, and now is also then fed to a SOFC or a PEMFC; in the latter
considered for syngas production in new GTL case an additional fuel-processing system is
(gas-to-liquid) plants [550]. ATR runs either on needed for CO removal.
Ni- or Rh-based catalysts, usually with alumina
or magnesium alumina supports to improve
thermal stability and strength at the high oper- 8.2. Ammonia Synthesis
ating temperatures. Current developments in- [48,557,534,558]
clude air-blown ATR, in which eliminating the
need for an oxygen plant is traded off by the In the Haber – Bosch process, ammonia is syn-
compression costs, in particular in GTL with FT. thesized over a promoted iron metal catalysts
ATR can also be operated without catalysts. from its constituents, nitrogen and hydrogen, at
There are a variety of proposed methods for approximately 400 C and 15 MPa (for more
syngas production from alternative feeds [551] details see also ! Ammonia).
such as ethanol or any other biomass-derived
fuel. In particular, CPOX and ATR techniques N2 þ3 H2 !2 NH3
84 Heterogeneous Catalysis and Solid Catalysts
Reactors with capacities up to 1000 t/d are used. active. These observations are consistent with
The reaction toward the target product NH3 is the earlier suggestion [561] that dinitrogen ad-
therefore thermodynamically favored at low sorption is an activated process and that it is the
temperature and high pressure. This equilibrium rate-determining step in the catalytic cycle.
limitation at practical conditions requires loop In contrast, the adsorption of dihydrogen on
operation with recovery of the easily condens- iron is fast and characterized by a high sticking
able product gas. The feed gases are prepared coefficient (ca. 101) and an extremely small
from air (nitrogen) and hydrogen via syngas (see activation barrier. This chemisorption is disso-
also Section Synthesis Gas and Hydrogen). ciative and yields covalently bonded H atoms
Besides Fe, only Ru has been found to be a which have high mobility on the iron surface.
practically useful catalyst, although thousand of Atomic nitrogen was shown to be the most
systems have been tested over the years [558]. stable and predominant chemisorbed species on
The most important single application of Fe(111) after evacuation [87,88], and it was
ammonia is the production of artificial fertilizer. inferred to be an intermediate in the catalytic
Ammonia is also required in the production of reaction. Adsorbed dinitrogen could be excluded
explosives, dyestuffs, plastics, and life-science as a reactive intermediate. The involvement of
products. In environmental catalysis, ammonia adsorbed N atoms in the rate-determining step was
is applied as reducing agent for nitrogen oxides also demonstrated by kinetics experiments [562].
emitted in power plants and more recently also Other less stable and less abundant surface inter-
in automotive vehicles (see also Section Envi- mediates include NH and NH2 species.
ronmental Catalysis). Based on these results the following se-
The mechanism of ammonia synthesis is one quence of elementary steps was formulated
of the best known in heterogeneous catalysis, (* denotes a surface site):
besides CO oxidation on Pt (see Chap. Theoreti-
cal Aspects), the reaction served as prototype for N2 þ2* !2 Nads ð36Þ
the understanding of heterogeneous catalysis by
elucidation of the molecular behavior on the H2 þ2* !2 Hads ð37Þ
catalytic surface, and represents one of the few
successful examples of bridging the materials Nads þHads !NHads þ* ð38Þ
and pressure gap between surface science and
industrial heterogeneous catalysis. Three Nobel
NHads þHads !NH2ads þ* ð39Þ
prizes in chemistry are closely related to ammo-
nia synthesis (HABER 1921, BOSCH 1931, ERTL
2007). Therefore, the mechanism of ammonia NH2ads þHads !NH3 þ2* ð40Þ
synthesis is discussed in more detail here. A schematic potential-energy diagram for the
The adsorption of N2 on iron is slow and is catalytic cycle is shown in Figure 27. Decompo-
characterized by a very low sticking coefficient sition of N2 is exothermic, whereas the steps
(ca. 106) and high activation energy [557]. involved in successive hydrogenation yielding
Single-crystal surfaces of iron are reconstructed NHx species are endothermic. The addition of
upon adsorption of nitrogen. Dinitrogen is dis- the first H atom is the most difficult step.
sociated above 630 K [559] and forms complex The promotion of the iron catalyst with
surface structures. These have been inferred to potassium lowers the activation energy for dis-
be surface nitrides with depths of several atomic sociative N2 chemisorption [563].
layers [557]. Their composition is roughly Fe4N.
The corresponding bulk compound is thermody-
namically unstable under conditions for which 8.3. Methanol and Fischer – Tropsch
the surface structure is stable. The rate of disso- Synthesis
ciative adsorption of dinitrogen is structure-sen-
sitive, the Fe(111) face being by far the most 8.3.1. Methanol Synthesis [148]
active, since the activation energy is the smallest
and the rate of adsorption the highest [560]. The Methanol is one of the most important organic
same crystal face is also the catalytically most chemicals (see also ! Methanol). It is mainly
Heterogeneous Catalysis and Solid Catalysts 85
Figure 27. Potential-energy diagram for the sequence of elementary steps of the ammonia synthesis reaction (energies in
kJ mol1) [234]
used as an intermediate for production of form- majority of methanol plants use this more ad-
aldehyde, methyl tert-butyl ether (MTBE), vanced low-pressure synthesis.
acetic acid, amines, and others. Methanol is Although methanol synthesis on copper-base
produced from synthesis gas according to the catalysts has been intensively studied for several
following stoichiometry. decades, no general agreement about the nature
of the active sites and the reaction mechanism
COþ2 H2 !CH3 OH could be achieved. Regarding the active site, it
It is now generally accepted that this reaction appears that metallic copper in close contact to
proceeds by conversion of CO via the water-gas ZnO is a requirement for an active and selective
shift reaction followed by hydrogenation of catalyst. This synergy has been explained by
carbon dioxide [564]. various mechanisms including hydrogen spill-
over from ZnO [565], stabilization of intermedi-
COþH2 O!H2 þCO2 ates on ZnO or the interface between Cu and
ZnO [566], and spreading of Cu on the ZnO
CO2 þ3 H2 !CH3 OH surface [567]. The most important intermediates
appear to be formate, methoxy, and formyl
All these reactions are exothermic and equilib- species. A possible reaction mechanism in-
rium-limited. The achievable methanol yield is volves dissociative adsorption of hydrogen, hy-
favored by high pressure and low temperature. drogenation of adsorbed CO to CO2, conversion
The first process for methanol synthesis, of atomic hydrogen to formate, further addition
operating at about 30 MPa and 300 – 400 C of hydrogen to give H2COO, hydrogenation of
over a Zn/Cr2O3 catalyst, was developed by this species to a methoxy species, and finally
BASF in Germany in 1923. A substantial im- hydrogenation of this group to methanol. Simu-
provement was made by ICI in the 1960s lations suggested that the rate-determining step
through introduction of the more active Cu/ in this sequence is hydrogenation of the H2COO
ZnO/Al2O3 catalyst, which allowed for synthe- species to the methoxy group [568].
sis under much milder reaction conditions of Several empirical and mechanistically based
50 – 100 bar and 200 – 300 C. Today, the vast rate equations for methanol synthesis have been
86 Heterogeneous Catalysis and Solid Catalysts
proposed. An example using only statistically in ! Coal Liquefaction. The most important
significant and physically meaningful para- reaction, which is exothermic with a reaction
meters is given in [569]. The usual catalyst enthalpy of about 150 kJ/mol, can be des-
geometry comprises pellets of typically five cribed by the following equation.
millimeters in size. Under the commercial reac-
tion conditions, pore diffusion resistances may n COþð2nþ1ÞH2 !Cn H2nþ2 þn H2 O
occur [570].
In industrial practice, a variety of different In side reactions, olefins and oxygenates are
reactor types for low-pressure methanol synthe- formed, and undesirable CO2 and additional
sis are used, but generally fixed beds of catalyst CH4 may be produced via the water-gas shift
operated in the gas phase are employed. One reaction and CO methanation.
possibility for temperature control during the FTS has a long history starting with FISCHER
exothermic reaction is a staged catalyst bed with and TROPSCH reporting the synthesis of liquid
interstage cooling through heat exchangers or hydrocarbons from synthesis gas under moder-
injection of cold synthesis gas. The other fre- ate conditions in 1923 [572]. Within a short
quently used possibility for exothermic reac- period, this new process was commercialized
tions is a cooled multitubular reactor with fixed and provided, together with coal liquefaction,
bed of catalyst in each tube. While the multi- synthetic fuel on a large scale in Germany
tubular reactor allows the best temperature con- during World War II. After the era of cheap oil
trol and thus the longest catalyst life, the capital began in the 1950s it became evident that FTS
costs for adiabatic reactors are lower. Two- was uneconomical at that time. Only South
phase fluidized-bed reactors and three-phase Africa continued production of fuels by FTS
reactors with an additional liquid product phase based on coal-derived synthesis gas for political
have also been extensively tested. However, the reasons. The 1973 oil crisis stimulated new
lack of mechanical stability and/or low catalyst interest in FTS, and Shell started development
effectiveness has until now prevented commer- of its middle distillate process. In 1993, the first
cial implementation of these reactor designs. plant based on natural gas came into operation in
Much effort has also been devoted to over- Malaysia. This gas-to-liquids (GTL) process is
coming the equilibrium-limited methanol con- currently being realized on industrial scale at
version in a single-pass reactor by removal of several sites. Commissioning of a plant with a
methanol from the reaction mixture. A particu- capacity of 70 000 barrels per day built by Sasol
larly interesting system removes methanol by and Qatar Petroleum took place in 2006 in
selective adsorption on a porous adsorbent trick- Qatar. Further large-scale industrial plants in
ling through a fixed-bed of catalyst [571]. How- Escravos, Nigeria (Sasol Chevron) and Qatar
ever, this elegant multifunctional reactor suffers (Shell, Qatar Petroleum) are under construction.
from severe practical mechanical problems. It appears that FTS will play a major role for the
Another approach concentrates on operation future production of synfuels based on alterna-
close to the dew point of the product to allow tive feedstocks (natural gas, coal, biomass).
removal of liquid methanol between beds of FTS has been considered as an ideal poly-
catalyst. In this case, highly active catalysts for merization reaction [573]. According to this
operation at very low temperature and high approach the distribution of mole fractions xn
pressure are required. of products can be described as a function of the
A possible future trend is the further proces- number of carbon atoms n in the chain.
sing of methanol to synthetic fuels via metha- xn ¼ ð1aÞan1
nol-to-olefins as proposed by Lurgi.
The ideal product composition depends only
on the chain-growth probability a, which is
8.3.2. Fischer – Tropsch Synthesis [148] determined by the catalyst used. In reality sig-
nificant deviations from ideal polymerization
Fischer – Tropsch synthesis (FTS) is the direct behavior are observed. Usually the methane
production of hydrocarbon chains from synthe- mole fraction is higher, while the ethene/ethane
sis gas. Details of the process can also be found mole fractions are lower than calculated. Many
Heterogeneous Catalysis and Solid Catalysts 87
mechanistic studies on FTS support the carbene 2 – 4 MPa and 220 – 240 C. Two reactor types
mechanism, which starts with the decomposi- are presently applied in low-temperature FTS: a
tion of CO and involves the insertion of methy- cooled fixed-bed reactor mainly used by Shell
lene (CH2) species into the growing alkyl and a slurry bubble column developed by Sasol.
chain [574]. Disadvantages of fixed-bed reactors are devel-
As FTS catalysts metals like iron, cobalt, and opment of a hot spot, low catalyst utilization due
ruthenium can be used [575]. Due to the high to pore diffusion, and, especially in case of gas
price of ruthenium only iron and cobalt have recycle for improved heat removal, high pres-
industrial relevance. A disadvantage of iron sure drop. On the other hand, mechanical stress
catalysts is kinetic inhibition by the co-product on catalyst particles, the need for separation of
water, whereas an advantage is the activity for solid catalyst and liquid products and highly
the water-gas shift reaction that allows the use demanding scaleup are drawbacks of slurry
of carbon-dioxide-containing or hydrogen- bubble column reactors. New trends in FTS
depleted synthesis gas mixtures [576]. Com- reactors are the use of monolith reactors for
pared to iron, cobalt catalysts are already active improved gas – liquid mass transfer [585] and
at lower reaction temperatures and have a dura- isothermal microstructured reactors.
bility of up to five years on stream compared
to about six months in the case of iron [577]. On
the other hand cobalt is more expensive than 8.4. Hydrocarbon Transformations
iron. In addition to the active component differ-
ent promoters (Pt, Pd, Ru, Re, K) can be em- 8.4.1. Selective Hydrocarbon Oxidation
ployed [578]. As carrier materials alumina, Reactions
silica, and titania can be utilized. Typical chain-
growth probabilities are 0.5 – 0.7 for iron and Selective hydrocarbon oxidation reactions
0.7 – 0.8 for cobalt [579]. Currently the deve- include several important classes of heteroge-
lopment of cobalt catalysts is aimed at maxi- neously catalyzed reactions, which find large-
mizing the chain-growth probability to values of scale industrial application for the synthesis of
up to 0.95 [580]. Since the product mixtures bulk chemicals. Reviews on the mechanisms of
obtained with these catalyst cannot directly used selective hydrocarbon oxidation [200], oxida-
and must be further processed to achieve the tive dehydrogenation of alkanes [586], ammox-
desired fractions (diesel and gasoline fuels), it idation of alkenes, aromatics and alkanes [63],
has been suggested to couple Fischer – Tropsch and epoxidation of alkenes [587] are available.
catalysts with hydrocracking catalysts in one Here, some mechanistic aspects of the epoxida-
reactor [581,582]. tion of alkenes and of the ammoxidation of
As liquid products often fill the pore system hydrocarbons are discussed.
of working catalysts, resistances caused by pore
diffusion may occur even with small catalyst 8.4.1.1. Epoxidation of Ethylene and Pro-
particles. Catalyst efficiency is significantly pene [587,588]
reduced at characteristic catalyst dimensions The epoxidation of ethylene by dioxygen is
above 100 mm [583]. Furthermore, the higher catalyzed by silver metal and yields ethylene
diffusion coefficient of hydrogen compared to oxide (! Ethylene Oxide), an important inter-
carbon monoxide increases the H2/CO ratio mediate for the synthesis of glycols and polyols.
inside the porous catalyst. This leads to an Total oxidation of the reactant and the
increase of the chain-termination probability target product limit the selectivity of the
and thus to a decrease in chain length of the
products [584].
The development of catalysts with very high
chain-growth probabilities resulted in the devel-
opment of the more advanced low-temperature
FTS, in which synthesis gas and liquid products
are present under reaction conditions. Industrial
reactors are operated at typical conditions of Scheme 1.
88 Heterogeneous Catalysis and Solid Catalysts
process. Scheme 1 shows the three competing the density of subsurface oxygen atoms is also
reactions. reduced so that the polarizability of oxygen
The catalyst therefore must be tuned such atoms adsorbed on the external surface is re-
that the optimal selectivity for ethylene oxide is duced. Consequently, these oxygen atoms be-
achieved. The active phase consists of large Ag have as nucleophilic oxygen atoms and tend
particles supported on low surface area a-Al2O3 to interact preferentially with hydrogen atoms
promoted by alkali metal salts. A beneficial of the ethylene molecule, thus leading to total
effect is also obtained by adding chlorine-con- oxidation. This situation is schematically shown
taining compounds such as vinyl chloride to the in Scheme 3 [587]. Therefore, epoxidation
reaction feed. Under reaction conditions this selectivity must decrease with decreasing oxy-
additive is readily combusted on silver, and gen coverage. The fact that vacant silver sites
chlorine is adsorbed on the metal surface. exist in the vicinity of an adsorbed oxygen
Oxygen can be adsorbed on transition metals atom at low coverage (see Scheme 3), is also
in general and on silver in particular in three detrimental.
different states: (1) molecular dioxygen, (2) The influence of alkali metal and chlorine
adsorbed atomic oxygen, and (3) subsurface modifiers is complex. The effect of chlorine is
atomic oxygen [588]. Molecular oxygen is sta- twofold: (1) it suppresses vacant silver sites, and
ble on an Ag(111) surface at temperatures below (2) it enhances the electron deficiency of silver.
ca. 220 K. It dissociates at higher temperatures. The latter effect is due to the ability of chlorine
Oxygen dissociation occurs at high-coordina- to also occupy subsurface positions [594] and
tion sites, since at least two neighboring metal thus to adopt the role of subsurface oxygen as
atoms must be available. It has been shown that illustrated in Scheme 4 [587]. These effects
ensembles with a minimum of five silver atoms improve the initial selectivity r1/r2 (ri denotes
are required [589,590]. Oxygen atoms adsorbed a reaction rate, see Scheme 1). The overall
originally on the external silver metal surface selectivity is also reduced by subsequent com-
may move to subsurface lattice positions. Sub- bustion of the epoxide (r3 in Scheme 1), partic-
surface oxygen atoms have been proved to form ularly at high conversions. The combustion
on transition metals including Rh, Pd, and of the epoxide is induced by the residual
Ag [591]. The maximum oxygen coverage on acidity of the a-Al2O3 support. The presence
silver surfaces is one oxygen atom per silver
atom, corresponding to the composition of
AgO [588].
The presence of subsurface oxygen atoms
reduces the electron density on adjacent silver
atoms. Hence, oxygen atoms adsorbed on the
external surface which share bonds to silver
surface atoms with subsurface oxygen atoms
become highly polarizable. When exposed to
ethylene, the interaction of the surface oxygen
atoms with the p electrons of ethylene leads to a
flow of electron density from the surface oxygen
atom to the positively charged surface silver Scheme 2.
atom [592]. The surface oxygen atoms behave
chemically as electrophilic oxygen atoms,
which preferentially react with the part of the
reactant molecule having the highest electron
density. This situation is most likely at high
oxygen coverages, consistent with the experi-
mental observation that the epoxidation selec-
tivity is dramatically enhanced by increasing
oxygen coverage [593]. Scheme 2 illustrates
this scenario [587]. At low oxygen coverages Scheme 3.
Heterogeneous Catalysis and Solid Catalysts 89
processes have been developed further by De- hydrocarbon, and the reduced solid is reoxi-
gussa and Uhde, as well as by BASF and Dow, dized by gas-phase oxygen (Mars – van Kreve-
and startup of first production plants is sched- len mechanism [601], see also [200]).
uled for 2008 [598]. Degussa and Uhde have The most important alkene ammoxidation is
also investigated the gas-phase epoxidation of that of propene to acrylonitrile (Sohio Acryloni-
propene. Due to the safety risks associated with trile Process, Eq. 44; see also ! Acrylonitrile–
mixtures of gaseous propene and hydrogen Quality Specifications and Chemical Analysis)
peroxide as well as the danger of hydrogen [586]
peroxide decomposition during evaporation,
new technical concepts based on microstruc- 2 CH2 ¼ CHCH3 þ 2 NH3 þ 3 O2 !2 CH2
tured devices had to be developed [495]. High ¼ CHCNþ6 H2 O (44)
productivities of more than 1 kg of propylene
oxide per kilogram of catalyst and hour could be Molybdates and antimonates can be used as
obtained at high propane-to-propene oxide se- catalysts for this reaction. The active sites are
lectivity of more than 90 %. If the decomposi- thought to have bifunctional nature [63,602,603].
tion of hydrogen peroxide can be significantly A generalized catalytic cycle for alkene ammoxi-
reduced, the gas-phase process could become dation is shown in Figure 28 [63]. Ammonia is
interesting alternative to the commercial liquid- proposed to interact first with the bifunctional
phase processes. active site generating an ammoxidation site. The
alkene coordinates to this site to form an allylic
8.4.1.2. Ammoxidation of Hydrocarbons intermediate. After several rearrangements and
[63,599,600] oxidation steps, the surface intermediate is trans-
In ammoxidation, ammonia reacts with a reduc- formed into the nitrile, which subsequently des-
ible organic molecule, most frequently an al- orbs. A reduced surface site is thus formed,
kene, alkane, or aromatic, in the presence of which is restored to its original fully oxidized
dioxygen to yield nitriles (e.g., Eq. 42). state by lattice oxygen O2, which is provided by
adjacent reoxidation sites. These sites then dis-
2 CH2 ¼ CRCH3 þ 2 NH3 þ 3 O2 !2 CH2 sociate dioxygen to lattice oxygen. The newly
¼ CRCN þ 6 H2 O (42) formed lattice oxygen then diffuses to the oxy-
gen-deficient reduced surface site, from where
The ammoxidation of an alkene is a six- vacancies simultaneously penetrate through the
electron oxidation that produces an unsaturated lattice of the solid to the reoxidation sites. Clear-
nitrile and water. The reaction is related to the ly, these sites must communicate with each other
four-electron oxidation of alkenes (Eq. 42) [75] via a common solid-state lattice which is capable
producing unsaturated aldehydes and water, and of facile transport of electron, anion vacancies,
to the two-electron oxydehydrogenation of al- and lattice oxygen [63]. As an example, the
kenes to dienes and water (Eq. 43) [75]. proposed bifunctional active site of Bi2MoO6
(see Section Metal Oxides) is schematically illu-
CH2 ¼ CRCH3 þ O2 !CH2 ¼ CRCHO þ H2 O strated in Figure 29 [213]. The various function-
alities were assigned to specific elements and to
2 CH2 ¼ CHCH2 CH2 R þ O2 !2 CH2 specific lattice oxygen positions. Bridging oxy-
¼ CHCH ¼ CHR þ 2 H2 O (43) gen atoms Bi–O–Mo are considered to be re-
sponsible for a-hydrogen abstraction from the
Catalysts for these reactions are complex alkene, while oxygen atoms associated with Mo
mixed metal oxides containing variable-valence are responsible for oxygen (Mo¼O) and nitrogen
elements (see Section Metal Oxides), the am- (Mo¼NH) insertion into an allylic intermediate.
moxidation catalysts typically being the most The oxygen dissociation and its reduction to
complex. These materials possess redox prop- lattice oxygen is assumed to occur in the
erties, i.e., they can readily be reduced by region of high electron density generated by the
ammonia and reoxidized by dioxygen present two lone pair electron orbitals of Bi–O–Bi
in the gas phase. It is the lattice oxygen of the sites. More easily reducible elements than Bi
catalyst which reacts with ammonia and the are Fe, Ce, U, and Cu, which are components of
Heterogeneous Catalysis and Solid Catalysts 91
more complex, multicomponent catalysts (see tive dehydrogenation of ethane to ethylene and
Section Metal Oxides) [63]. As an illustration of for ammoxidation of propane to acrylonitrile.
the mechanisms of ammoxidation and selective
oxidation of propene, Figure 30 shows the pro- 8.4.2. Hydroprocessing Reactions [49,273,
posed catalytic cycles for the two reactions [604]. 274,606,607–148]
More recently, selective catalytic oxidation
and ammoxidation of alkanes as lower cost (see also ! Oil Refining–Environmental Pro-
alternatives to alkenes has attracted consider- tection in Oil Refining)
able interest [600,605]. Multicomponent metal Hydroprocessing treatment, including hy-
oxide catalysts have been intensively studied. drodesulfurization (HDS), hydrodenitrogena-
Promising results have been obtained especially tion (HDN), hydrodeoxygenation (HDO),
with the MoV – TeNbO system, both for oxida- hydrometalation (HDM), hydrogenation, and
hydrocracking, are among the largest industrial
processes in terms of catalyst consumption.
Crude petroleum contains particularly organo-
sulfur and organonitrogen compounds, which
are most abundant in heavy petroleum fractions.
These contaminants must be removed for envi-
ronmental reasons. The reactions take place in
the presence of H2 at high temperatures (ca.
600 – 700 K) and pressures of 500 kPa to
1 MPa. Because of the lower reactivity of or-
Figure 29. Schematic representation of the active site of ganonitrogen compounds as compared to orga-
Bi2MoO6 [446] nosulfur compounds, the reaction conditions are
O0 ¼ Oxygen responsible for a-H abstraction; O00 ¼ Oxy- more severe for HDN than for HDS.
gen associated with Mo; responsible for oxygen insertion
into the allylic intermediate; f ¼ Proposed center for O2 Catalysts for hydroprocessing are highly dis-
reduction and dissociative chemisorption. persed metal sulfides (mainly MoS2, but also
92 Heterogeneous Catalysis and Solid Catalysts
Figure 30. Mechanism of selective ammoxidation and oxidation of propene over bismuth molybdate catalysts [604]
WS2) supported on g-Al2O3. The materials are selectivity, however, drops sharply as the H2S
promoted by cobalt or nickel, depending on concentration in the feed increases.
application. Hydroprocessing reactions accompanying
Although the detailed mechanisms have not hydrogenation and hydrodesulfurization include
yet been elucidated, significant progress in un- hydrodenitrogenation, whereby organonitrogen
derstanding the chemistry of the various hydro- compounds in the feed react with H2 to give NH3
processing reactions at a molecular level has and hydrocarbons. As an example, a reaction
been made [49,273,274,607,608]. In the follow- network for the hydroprocessing of quinoline is
ing, however, the focus is on reaction networks shown in Figure 32 [606]. The supported metal
of several hydroprocessing reactions with pseu- sulfide catalysts are much less selective for
do-first-order rate constants for individual reac- nitrogen removal than for sulfur removal.
tion steps. Hydroprocessing reactions are carried out in
The organosulfur compounds in petroleum different reactor types [610]. The most common-
include sulfides, disulfides, and aromatics (in- ly used is a fixed-bed reactor operated in the
cluding thiophene, benzothiophene, dibenzo- trickle-flow regime with cocurrent up- or down-
thiophene, and related compounds). Benzo- and flow of gas and liquid. Alternative reactor de-
dibenzothiophene are predominant in heavy signs are moving-bed and ebullated-bed reactors
fuels. The reaction network for hydrodesulfur- with greater flexibility, e.g., owing to easy re-
ization of dibenzothiophene, a representative placement of spent catalyst during operation.
member of organosulfur contaminants in fuel, Recently, structured packed columns of mono-
is shown in Figure 31 [609]. Hydrogenation and lithic catalysts operated in countercurrent mode
hydrogenolysis take place in parallel. The latter are gaining importance in hydroprocessing re-
reaction is essentially irreversible and leads to search, because higher conversions can be ob-
the formation of H2S and biphenyl. At low H2S tained. A future trend is the development of
concentrations in the feed, the sulfide catalysts processes for the treatment of increasingly heavy
are highly selective for hydrogenolysis. The oils and of various residues [611].
Heterogeneous Catalysis and Solid Catalysts 93
Figure 31. Reaction network for hydrodesulfurization and hydrogenation of dibenzothiophene catalyzed by sulfided Co –
Mo/Al2O3 at 570 K and 10 MPa [609]
Numbers next to the arrows represent the pseudo-first-order rate constants in units of L/(g of catalyst s) when the H2S
concentration is very small. Addition of H2S markedly decreases the selectivity for hydrodesulfurization.
Figure 32. Reaction network for hydrogenation and the hydrogenolysis of quinoline catalyzed by sulfided Ni – Mo/g-Al2O3
at 620 K and 3.5 MPa [606]
Numbers next to the arrows represent the pseudo-first-order rate constants in units of L/(g of catalyst s) when the H2S
concentration is small but sufficient to maintain the catalysts in the sulfided forms.
94 Heterogeneous Catalysis and Solid Catalysts
8.5. Environmental Catalysis for two main reasons. Firstly, it is only moder-
ately sulfated under real exhaust gas conditions,
8.5.1. Catalytic Reduction of Nitrogen and catalytic activity even increases after sulfa-
Oxides from Stationary Sources [313] tion [616]. Secondly, vanadia is able to spread in
thin layers on the anatase support to give highly
Fossil fuels such as coal, oil, gas, and others are active structures with large surface area. How-
burnt or gasified for energy conversion. In ever, the amount of vanadia in technical cata-
Western European countries and Japan mea- lysts is limited to only a few weight percent,
sures have been implemented since 1980 for because it is also catalytically active for SO2
reducing emissions, especially of NOx from oxidation.
power plants. The preferred method to remove The mechanism of the standard SCR reac-
NOx from exhaust gases of power plants, indus- tion over vanadia-based catalysts is generally
trial boilers, and gas turbines is based on the so- assumed to proceed via an Eley – Rideal
called selective catalytic reduction (SCR) with mechanism involving adsorbed ammonia and
ammonia in the presence of oxygen. The stoi- gas-phase NO. Based on this mechanism, the
chiometry of the main desired reactions can be following rate equation can be derived that
described as follows: has been successfully used to model the SCR
reaction.
4 NOþ4 NH3 þO2 !4 N2 þ6 H2 O ðstandard KNH3 cNH3 cNO
rNO ¼ k
SCRÞ ð1þKNH3 cNH3 Þ
6 NO2 þ8 NH3 !7 N2 þ12H2 O ðNO2 SCRÞ Water vapor has an additional inhibiting
effect on the rate of NO removal. In recent
NOþNO2 þ2 NH3 !2 N2 þ3 H2 O ðfast SCRÞ studies, it was also possible to model and simu-
late the transient behavior of SCR catalysts
The standard SCR reaction is most important exposed to changes in reactant concentration
if NOx originates from high-temperature com- and temperature [313].
bustion processes, where very little NO2 is As the rate of the SCR reaction under indus-
present. However, in exhaust streams containing trially relevant conditions is quite high, external
higher amounts of nitrogen dioxide, the fast and intraparticle diffusion resistances play an
SCR reaction, which proceeds at least ten times important role, especially for the frequently
faster than the standard SCR reaction, may used honeycomb monolith or plate-type cata-
become the predominant reaction [612]. lysts operating in laminar flow regime. These
At higher temperatures above ca. 450 C, the geometries must be used to minimize the pres-
reducing agent ammonia reacts with oxygen in sure drop over the catalyst bed. Monolithic
undesirable parallel reaction to give the pro- elements usually have channel sized of 3 –
ducts N2, N2O, or NO. On the other hand, at 7 mm, cross sections of 15 15 cm, and
temperatures below 200 C, ammonia and NOx lengths of 70 – 100 cm. Monoliths or packages
may form solid deposits of ammonium nitrate of plate catalysts are assembled into standard
and nitrite. modules, which are then placed in the SCR
The SCR of nitrogen oxides was first carried reactors as layers. These modules can be easily
out with Pt catalysts [613]. Due to the high replaced to introduce fresh or regenerated
nitrous oxide selectivity of this catalyst, base catalysts.
metal catalysts have been developed for NOx SCR reactors can be used in different con-
reduction. Vanadia supported on titania (in the figurations, depending on fuel type, flue gas
anatase form) and promoted with tungsten or composition, NOx threshold, and other factors.
molybdenum oxide exhibits the best catalytic The first possibility is the location directly after
properties. While BASF was the first to describe the boiler (high-dust arrangement) where the
vanadia as active component for SCR [614], flue gas usually has the optimal temperature for
TiO2-supported vanadia for treatment of ex- the catalytic reaction. On the other hand, dust
haust gases was developed in Japan [615]. Ana- deposition and erosion as well as catalyst deac-
tase is the preferred support for SCR catalysts tivation are more pronounced than in other
Heterogeneous Catalysis and Solid Catalysts 95
coverage. The transfer of TWC technology to basic components of the NSC, mainly on
lean-burn gasoline and diesel motors is prob- barium carbonate to form the nitrate. When
lematic because of the insufficient NOx abate- the storage capacity is reached, the engine
ment. This is associated with the lower raw is operated under rich conditions for a few
emissions of reducing agents as well as the high seconds to give an exhaust containing CO,
content of O2, which enhances oxidation of HC HC, and H2 as reducing agents for catalyst
and CO and thus suppresses NOx reduction. regeneration (back-transformation of the ni-
Therefore, alternative concepts are required for trate to the carbonate).The effect of the Ba
the reduction of NOx under lean-burn condi- component is to adsorb NOx at temperatures
tions. For this purpose selective catalytic re- above 250 C, whereas substantial storage is
duction by NH3 and NOx storage and reduction also provided by Al2O3 and CeO2 at lower
catalysts are being considered in the automo- temperatures [626].
tive industry.
Catalytic CO oxidation Catalytic CO
Selective Catalytic Reduction (SCR) of NOx oxidation is an essential reaction of TWC and
by Ammonia. The SCR procedure is the NSC and has also applied in diesel engines
only technique that selectively converts NOx to since the 1990s in the so-called direct oxidation
N2, even under strongly oxidizing conditions. catalyst (DOC). Furthermore, the catalytic
Thus, SCR has been considered as the technol- abatement of CO is also a state-of-the-art tech-
ogy of choice for NOx removal in lean-burn nology for gas turbine engines fed by natural
engines. Indeed, the SCR process covers the gas. DOCs usually contain Pt as an active
relevant temperature range of diesel engines and component showing outstanding performance.
provides effective NOx abatement. Thus, SCR The expensive platinum can be substituted by
has advanced to a state-of-the-art technology for the less active but cheaper palladium. The
heavy-duty vehicles. However, in mobile appli- precious metal load of a DOC is ca. 3 g L1.
cations the storage of NH3 is a problem. There- DOCs also oxidize gaseous HC and HC ad-
fore, an aqueous solution of urea (32.5 wt %) sorbed on soot particles.
called AdBlue is currently used. The urea solu-
tion is sprayed into the tailpipe, where ammonia Removal of Soot The diesel particulate
is produced after thermolysis and hydrolysis of filter (DPF) is used for the removal of soot from
the vaporizing urea – water droplets. Current diesel exhaust. DPFs mechanically separate
research focuses on optimization of the dosing the particles by forcing the exhaust gas to
system and the development of vanadia-free diffuse through porous walls thus leading to
catalysts, for instance, by substitution with high filtration efficiency [627]. The DPF ap-
Fe-ZSM5 zeolites [622]. Alternative reducing plication requires regeneration, i.e., oxidation
agents such as hydrocarbons and hydrogen has of the stored soot particles. Soot deposits can
been discussed as well. produce a substantial backpressure leading to
increased fuel consumption and decreased en-
NOx Storage Reduction Catalysts NOx gine efficiency. The preferred method for DPF
storage reduction catalysts (NSC) were origi- regeneration is the CRT (continuously regen-
nally developed for lean spark-ignition en- erating trap) technology involving the initia-
gines and are currently being transferred to tion of soot oxidation by NO2 produced by
diesel passenger cars. The NSC procedure is oxidation of NO on Pt catalysts, as in NSC
based on periodic adsorption and reduction of and SCR. The Pt catalyst can be applied in form
NOx [625]. The catalysts consist of Pt, Pd, and of a precatalyst, and coating on the DPF. Fur-
Rh in the mass ratio of approximately 10/5/1 thermore, so-called fuel-borne catalysts
with a total precious metal load of ca. 4 g L1. (FBC), which are organometallic compounds
NSCs contain basic adsorbents like Al2O3 based on Ce or Fe, e.g., ferrocene, can be added
(160 g L1), CeO2 (98 g L1) and BaCO3 to the fuel [628]. FBCs also decrease soot
(29 g L1, as BaO equivalent) [626]. In the emissions from the engine by direct oxidation
lean phase of the engine (general operation of soot in the engine. Additionally, they are
mode), NOx of the exhaust is adsorbed on the embedded in the soot particles.
Heterogeneous Catalysis and Solid Catalysts 97
146 S. Romet, M. F. Couturier, T. K. Whidden, J. 169 M. Che, O. Clause, Ch. Marcilly in G. Ertl, H.
Electrochem. Soc. 148 (2001) G82. Kn€ ozinger, J. Weitkamp (eds.): Handbook of
147 C. D. Scott, A. Povitsky, C. Dateo, T. Gokcen, P. Heterogeneous Catalysis, Vol. 1, Wiley-VCH,
A. Willis, R. E. Smalley, J. Nanosci. Nanotech- Weinheim 1997, p. 191.
nol. 3 (2003) 63. 170 J. P. Brunelle, Pure Appl. Chem. 50 (1978) 1211.
148 C. H. Bartholomew, R. J. Farrauto: Fundamen- 171 B. G. Linsen (ed.): Physical and Chemical As-
tals of Industrial Catalytic Processes, 2nd ed., pects of Adsorbents and Catalysts, Academic
Wiley, Hobboken 2006. Press, New York 1970.
149 S. Senkan, Angew. Chem. 113 (2001) 322;An- 172 H. Kn€ ozinger, P. Ratnasamy, Catal. Rev.-Sci.
gew. Chem. Int. Ed. 40 (2001) 312. Eng. 17 (1978) 31.
150 B. Jandeleit, D. J. Schaefer, T. S. Powers, H. W. 173 H. Oechsner, Scanning Microsc. 2 (1988) 9.
Turner, H. W. Weinberg, Angew. Chem. 111 (1999) 174 H. P. Boehm, H. Kn€ ozinger in J. R. Anderson, M.
2649;Angew. Chem. Int. Ed. 38 (1999) 2494. Boudart (eds.): Catalysis: Science and Technol-
151 J. N. Cawse, Acc. Chem. Res. 34 (2001) 313. ogy, Vol. 4, Springer, Berlin 1983, p. 39.
152 C. Hoffmann, H.-W. Schmidt, F. Sch€uth, J. 175 C. S. John, M. S. Scurrell: Catalysis, The Chem-
Catal. 198 (2001) 348. ical Society, London, 1 (1977) 136.
153 S. I. Woo, K. W. Kim, H. Y. Cho, K. S. Oh, M. K. 176 J. Wagner, W. Nehb in G. Ertl, H. Kn€ ozinger, J.
Jeon, N. H. Tarte, T. S. Kim, A. Mahmood, Weitkamp (eds.): Handbook of Heterogeneous
QSAR Comb. Sci. 24 (2005) 138. Catalysis, Vol. 4, Wiley-VCH, Weinheim 1997,
154 A. Hagemeyer, P. Strasser, A. F Volpe, Jr. (eds.): p. 1761.
High Throughput Screening in Chemical Catal- 177 E. F. Vansant, P. Van Der Voort, K. C. Vrancken
ysis, Wiley-VCH, Weinheim 2004. (eds.): Stud. Surf. Sci. Catal. 93 (1995).
155 O. Trapp, J. Chromatogr. A 1184 (2008) 160. 178 A. E. Legrand (ed.): The Surface Properties of
156 U. Rodemerck, M. Baerns, M. Holena, D. Wolf, Silicas, Wiley, Chichester, New York, Wein-
Appl. Surf. Sci. 223 (2004) 168. heim, Brisbane, Singapore, Toronto 1998.
157 O. Trapp, S. K. Weber, S. Bauch, W. Hofstadt, 179 H. Kn€ ozinger in P. Schuster, G. Zundel, C.
Angew. Chem. Int. Ed. 46 (2007) 7307. Sandorfy (eds.): The Hydrogen Bond, Vol. 3,
158 M. Baerns, E. K€orting in G. Ertl, H. Kn€ozinger, North Holland, Amsterdam 1976, p. 1263.
J. Weitkamp (eds.): Handbook of Heterogeneous 180 J. M. Thomas, R. G. Bell, C. R. A. Catlow in G.
Catalysis, Vol. 1, Wiley-VCH, Weinheim 1997, Ertl, H. Kn€ ozinger, J. Weitkamp (eds.): Hand-
p. 419. book of Heterogeneous Catalysis, Vol. 1, Wiley-
159 D. Wolf, O. V. Buyevskaya, M. Baerns, Appl. VCH, Weinheim 1997, p. 286.
Catal. A: General 200 (2000) 63. 181 C. T. Kresge, M. E. Leonowicz, W. J. Roth, J. C.
160 K. Kochloefl, Chem. Eng. Technol. 24 (2001) 3. Vartuli, J. S. Beck, Nature 359 (1992) 710.
161 J. Greeley, J. K. Nørskov, M. Mavrikakis, Annu. 182 J. S. Beck, J. C. Vartuli, W. J. Roth, M. E.
Rev. Phys. Chem. 53 (2002) 319. Leonowicz, C. T. Kresge, K. D. Schmidt, C.
162 C. J. H. Jacobsen, S. Dahl, B. S. Clausen, S. T. W. Chu, D. H. Olson, E. W. Sheppard, S. B.
Bahn, A. Logadottir, J. K. Nørskov, J. Am. McCullan, J. B. Higgins, J. L. Schlenker, J. Am.
Chem. Soc. 123 (2001) 8404. Chem. Soc. 114 (1992) 10834.
163 B. C. Gates: Catalytic Chemistry, Wiley, New 183 E. A. Colbourn, W. C. Mackrodt, Surf. Sci. 143
York 1992. (1984) 391.
164 C. N. Satterfield: Heterogeneous Catalysis in 184 S. Coluccia, A. J. Tench: Proc. 7th Intern. Congr.
Industrial Practice, McGraw-Hill, New York Catal., Tokyo, 1980, Kodansha, Tokyo, Elsevier,
1991. Amsterdam 1981, p. 1154.
165 R. J. Farrauto, C. H. Bartholomew: Fundamen- 185 A. Zecchina, D. Scarano, S. Bordiga, G. Spoto,
tals of Industrial Catalytic Processes, Blackie C. Lamberti, Adv. Catal. 46 (2001) 265.
Academic and Professional, London 1997. 186 R.N.Spitz,J.E.Barton,M.A.Barteau,R.H.Staley,
166 G. Ertl, H. Kn€ozinger, J. Weitkamp (eds.): Hand- A. W. Sleight, J. Phys. Chem. 90 (1986) 4067.
book of Heterogeneous Catalysis,Vols. 1 – 5, 187 A. Zecchina, M. G. Lofthouse, F. S. Stone, J.
Wiley-VCH, Weinheim 1997. Chem. Soc. Faraday Trans. 1 71 (1975) 1476.
167 J. Hagen: Industrial Catalysis, A Practical Ap- 188 S. Coluccia, A. M. Deane, A. J. Tench, J. Chem.
proach, Wiley-VCH, Weinheim 1999. Soc. Faraday Trans. 1 74 (1978) 2913.
168 K. Tanabe: Solid Acids and Bases, Kodansha, 189 H. Kn€ ozinger, Science 287 (2000) 1407.
Tokyo, Academic Press, New York, London 190 A. Cimino, F. S. Stone in G. Ertl, H. Kn€ ozinger,
1970. J. Weitkamp (eds.): Handbook of Heterogeneous
Heterogeneous Catalysis and Solid Catalysts 101
Catalysis, Vol. 2, Wiley-VCH, Weinheim 1997, Catalysis, Vol. 1, Wiley-VCH, Weinheim 1997,
p. 845. p. 100.
191 C. N. R. Rao, B. Raveau: Transition Metal 211 R. K. Grasselli, J. F. Brazdil: Solid State Chem-
Oxides, VCH, Weinheim 1995. istry in Catalysis, ACS Symposium Series,
192 P. A. Cox: Transition Metal Oxides, Clarendon Amer. Chem. Soc., Washington, 279 (1985).
Press, Oxford 1995. 212 J. Haber, G. Ertl, H. Kn€ ozinger, J. Weitkamp
193 H. H. Kung: Transition Metal Oxides: Surface (eds.): Handbook of Heterogeneous Catalysis,
Chemistry and Catalysis, Elsevier, Amsterdam Vol. 5, Wiley-VCH, Weinheim 1997, p. 2253.
1995. 213 R. K. Grasselli, J. Chem. Ed. 63 (1986) 216.
194 P. Pichat in G. Ertl, H. Kn€ozinger, J. Weitkamp 214 M. Egasihra, K. Matsuo, S. Kawaga, T. Seiyama,
(eds.): Handbook of Heterogeneous Catalysis, J. Catal. 58 (1979) 409.
Vol. 4, Wiley-VCH, Weinheim 1997, p. 2111. 215 US 4 370 279, 1983(Y. Sasaki, T. Nakamura, Y.
195 A. L. Linsebigler, G. Lu, J. T. Yates, Jr., Chem. Nakamura, K. Moriya, H. Utsumi, S. Saito).
Rev. 95 (1995) 735. 216 A. W. Sleight in J. J. Burton, R. L. Garten (eds.):
196 K. Arata, Adv. Catal. 37 (1990) 165. Advanced Materials in Catalysis, Academic
197 W. G€opel, K. D. Schierbaum in G. Ertl, H. Press, New York 1977, p. 181.
Kn€ozinger, J. Weitkamp (eds.): Handbook of 217 L. G. Tejuca, J. L. G. Fierro: Properties and
Heterogeneous Catalysis, Vol. 3, Wiley-VCH, Applications of Perovskite-type Oxides, M. Dek-
Weinheim 1997, p. 1284. ker, New York 1993.
198 K. Kochloefl in G. Ertl, H. Kn€ozinger, J. Weit- 218 P. Cavani, F. Trifiró, A. Vaccari, Catal. Today 11
kamp (eds.): Handbook of Heterogeneous Ca- (1991) 173.
talysis, Vol. 4, Wiley-VCH, Weinheim 1997, 219 F. Basile, M. Campanati, E. Serwicka, A. Vac-
p. 1831. cari, Appl. Clay Sci. 18 (2001) 1.
199 K. Kochloefl in G. Ertl, H. Kn€ozinger, J. Weit- 220 P. Gouzerh, A. Proust, Chem. Rev. 98 (1998) 77.
kamp (eds.): Handbook of Heterogeneous Ca- 221 E. Coronado, C. J. Gómez-Garcıa, Chem. Rev. 98
talysis, Vol. 5, Wiley-VCH, Weinheim 1997, (1998) 273.
p. 2151. 222 K.-Y. Lee, M. Misono in G. Ertl, H. Kn€ ozinger, J.
200 J. Haber in G. Ertl, H. Kn€ozinger, J. Weitkamp Weitkamp (eds.): Handbook of Heterogeneous
(eds.): Handbook of Heterogeneous Catalysis, Catalysis, Vol. 1, Wiley-VCH, Weinheim 1997,
Vol. 5, Wiley-VCH, Weinheim 1997, p. 2253. p. 118.
201 M. Muhler in G. Ertl, H. Kn€ozinger, J. Weitkamp 223 M. Misono, Catal. Rev.-Sci. Eng. 30 (1988) 339.
(eds.): Handbook of Heterogeneous Catalysis, 224 J. B. Moffat: Metal-Oxygen Clusters, Kluwer
Vol. 5, Wiley-VCH, Weinheim 1997, p. 2274. Academic/Plenum Publishers, New York 2001.
202 R. M. Barrer: Hydrothermal Chemistry of Zeo- 225 J. A. Gamelas, F. A. S. Couto, M. C. N. Trovao,
lites, Academic Press, London 1982. A. M. V. Cavaleiro, J. A. S. Cavaleiro, M.
203 W. M. Meier, D. H. Olson, Ch. Baerlocher: Atlas Guelton, Thermochim. Acta 326 (1999) 165.
of Zeolite Structure Types, 4th Ed., Butterworth- 226 T. Okuhara, M. Yamashita, K. Na, M. Misono,
Heinemann, London 1996. Chem. Lett.(1994) 1450.
204 J. Weitkamp, Solid State Ionics 131 (2000) 175. 227 Y. Izumi, M. Ogawa, W. Nohara, K. Krabe,
205 G. Bellussi, V. Fattore in P. A. Jacobs, N. Jaeger, Chem. Lett.(1992) 1987.
L. Kubelkova, B. Wichterlova (eds.): Zeolite 228 G. Centi, J. L. Nieto, C. Iapalucci, K. Br€
uckman,
Chemistry and Catalysis, Elsevier, Amsterdam E. M. Serwicka, Appl. Catal. 46 (1989) 197.
1991, p. 79. 229 F. Cavani, M. Koutyrev, F. Trifiró, Catal. Today
206 D. Barthomeuf, Catal. Rev.-Sci. Eng. 38 (1996) 28 (1996) 319.
521. 230 E. Wagner, T. Fetzer in G. Ertl, H. Kn€ ozinger, J.
207 J. M. Thomas, R. G. Bell, C. R. A. Catlow, G. Weitkamp (eds.): Handbook of Heterogeneous
Ertl, H. Kn€ozinger, J. Weitkamp (eds.): Hand- Catalysis, Vol. 4, Wiley-VCH, Weinheim 1997,
book of Heterogeneous Catalysis, Vol. 1, Wiley- p. 1748.
VCH, Weinheim 1997, p. 286. 231 M. S. Wainright in G. Ertl, H. Kn€ ozinger, J.
208 T. Ishihara, H. Takita, Catalysis 12 (1996) 21. Weitkamp (eds.): Handbook of Heterogeneous
209 J. J. Fripiat in G. Ertl, H. Kn€ozinger, J. Weitkamp Catalysis, Vol. 1, Wiley-VCH, Weinheim, Ger-
(eds.): Handbook of Heterogeneous Catalysis, many 1997, p. 64.
Vol. 1, Wiley-VCH, Weinheim 1997, p. 387. 232 R. Schl€ogl in G. Ertl, H. Kn€
ozinger, J. Weitkamp
210 P. G. Menon, B. Delmon in G. Ertl, H. Kn€ozinger, (eds.): Handbook of Heterogeneous Catalysis,
J. Weitkamp (eds.): Handbook of Heterogeneous Vol. 1, Wiley-VCH, Weinheim 1997, p. 54.
102 Heterogeneous Catalysis and Solid Catalysts
233 A. Baiker in G. Ertl, H. Kn€ozinger, J. Weitkamp 253 U. Mueller, M. Schubert, F. Teich, H. P€ utter, K.
(eds.): Handbook of Heterogeneous Catalysis, Schierle-Arnd, J. Pastre, J. Mater. Chem. 16
Vol. 2, Wiley-VCH, Weinheim 1997, p. 803. (2006) 626.
234 J. R. Jennings (ed.): Catalytic Ammonia Synthe- 254 F. X. L. I. Xamena, A. Abad, A. Corma, H.
sis: Fundamentals and Practice, Plenum Press, Garcia, J. Catal. 250 (2007) 294.
New York 1991. 255 M. J. Ledoux, C. Pham-Huu, CATTECH 5
235 S. T. Oyama in G. Ertl, H. Kn€ozinger, J. Weit- (2001) 226.
kamp (eds.): Handbook of Heterogeneous Ca- 256 H. Sieber, C. Hoffmann, A. Kaindl, P. Greil, Adv.
talysis, Vol. 1, Wiley-VCH, Weinheim 1997, Eng. Mater. 2 (2000) 105.
p. 132. in ref. [4], p. 132. 257 J. L. Williams, Catal. Today 69 (2001) 3.
236 C. Bouchy, C. Pham-Huu, B. Heinrich, C. Chau- 258 M. Valentini, G. Groppi, C. Cristiani, M. Levi, E.
mot, M. J. Ledoux, J. Catal. 190 (2000) 92. Tronconi, P. Forzatti, Catal. Today 69 (2001) 307.
237 R. Schl€ogl in G. Ertl, H. Kn€ozinger, J. Weitkamp 259 E. S. J. Lox, B. H. Engler in G. Ertl, H. Kn€ ozin-
(eds.): Handbook of Heterogeneous Catalysis, ger, J. Weitkamp (eds.): Handbook of Heteroge-
Vol. 1, Wiley-VCH, Weinheim 1997, p. 138. neous Catalysis, Vol. 4, Wiley-VCH, Weinheim
238 H. J€untgen, H. K€ uhl, Chem. Phys. Carbon 22 1997, p. 1569.
(1990) 145. 260 J. M. Thomas, Angew. Chem. 111 (1999) 380;
239 L. R. Radovic, F. Rodriguez-Reinoso, Chem. Angew. Chem. Int. Ed. 38 (1999) 3588.
Phys. Carbon 35 (1997) 243. 261 A. Stein, B. J. Melde, R. C. Schroden, Adv.
240 P. Serp, M. Corria, P. Kalck, Appl. Catal. A: Mater. 12 (2000) 1403.
General 253 (2003) 337. 262 D. E. De Vos, B. F. Sels, P. A. Jacobs, Adv. Catal.
241 R. P. Raffaelle, B. J. Landi, J. D. Harris, S. G. 46 (2001) 2.
Bailey, A. F. Hepp, Mater. Sci. Eng. B 116 (2005) 263 D. C. Sherrington, A. P. Kybett (eds.): Supported
233. Catalysts and their Applications, The Royal
242 F. de Dardel, T. V. Arden: Ullmann’s Encyclo- Society of Chemistry, Cambridge 2001.
pedia of Industrial Chemistry, 5th ed., Vol. 264 B. K. Hodnett, A. Kybett, J. H. Clark, K. Smith:
A 14, VCH Verlagsgesellschaft, Weinheim Supported Reagents and Catalysts in Chemistry,
1987, p. 393. The Royal Society of Chemistry, Cambridge
243 A. St€uwe, C.-P. H€alsig, H. Tschorn in G. Ertl, H. 1998.
Kn€ozinger, J. Weitkamp (eds.): Handbook of 265 B. Clapham, T. . Reger, K. D. Janda, Tetrahedron
Heterogeneous Catalysis, Vol. 4, Wiley-VCH, 57 (2001) 4637.
Weinheim 1997, p. 1986. 266 W. Keim, B. Driessen-H€ olscher in G. Ertl, H.
244 G. A. Olah, A. Molnar: Hydrocarbon Chemistry, Kn€ ozinger, J. Weitkamp (eds.): Handbook of
Wiley, New York 1995. Heterogeneous Catalysis, Vol. 1, Wiley-VCH,
245 J.-P. Vigneron in G. Ertl, H. Kn€ozinger, J. Weinheim 1997, p. 231.
Weitkamp (eds.): Handbook of Heterogeneous 267 I. E. Wachs: Catalysis, Vol. 13, The Royal
Catalysis, Vol. 2, Wiley-VCH, Weinheim Society of Chemistry, Cambridge 1997, p. 37.
1997, p. 888. 268 B. Delmon in G. Ertl, H. Kn€ ozinger, J. Weitkamp
246 K. Morihara, S. Doi, M. Takiguchi, T. Shimada, (eds.): Handbook of Heterogeneous Catalysis,
Bull. Chem. Soc. Jpn. 66 (1993) 2977. Vol. 1, Wiley-VCH, Weinheim 1997, p. 264.
247 G. Wulff in C. G. Gebelein (ed.): Biomimetic 269 G. C. Bond, J. C. Vedrine, Catal. Today 20
Polymers, Plenum Press, New York, 1990, p. 1. (1994) 1.
248 K. Morihara, M. Takaguchi, T. Shimada, Bull. 270 G. Centi, Appl. Catal. A: General 147 (1996) 267.
Chem. Soc. Jpn. 67 (1994) 1078. 271 F. J. Janssen in G. Ertl, H. Kn€ozinger, J. Weitkamp
249 M. Eddaoudi, D. B. Moler, H. L. Li, B. L. Chen, (eds.): Handbook of Heterogeneous Catalysis,
T. M. Reineke, M. O’Keefe, O. M. Yaghi, Acc. Vol. 4, Wiley-VCH, Weinheim 1997, p. 1633.
Chem. Res. 34 (2001) 319. 272 J. F. Armor, Chem. Mat. 6 (1994) 730.
250 S. Kaskel in F. Sch€uth, K. S. W. Sing, J. Weit- 273 R. Prins in G. Ertl, H. Kn€ ozinger, J. Weitkamp
kamp (eds.): Handbook of Porous Solids, Vol. 2, (eds.): Handbook of Heterogeneous Catalysis,
Wiley-VCH, Weinheim, 2002, p. 1190. Vol. 4, Wiley-VCH, Weinheim 1997, p. 1908.
251 H. Li, M. Eddaoudi, M. O’Keefe, O. M. Yaghi, 274 R. Prins, Adv. Catal. 46 (2001) 399.
Nature 402 (1999) 276. 275 M. Hino, K. Arata: Chem. Commun. 1988, 1259.
252 H. K. Chae, D. Y. Siberio-Perez, J. Kim, Y. Go, 276 S. Kuba, P. Concepcion, R. K. Grasselli, B. C.
M. Eddaoudi, A. J. Matzger, M. O’Keefe, O. M. Gates, M. Che, H. Kn€ ozinger, Phys. Chem.
Yaghi, Nature 427 (2004) 523. Chem. Phys. 3 (2001) 146.
Heterogeneous Catalysis and Solid Catalysts 103
277 S. Kuba, B. C. Gates, P. Vijayanand, R. K. Grass- 299 B. Cornils, W. A. Herrmann: Applied Homoge-
elli, H. Kn€ozinger: Chem. Commun. 2001, 57. neous Catalysis with Organometallic Com-
278 J. C. Mol in G. Ertl, H. Kn€ozinger, J. Weitkamp pounds, Wiley-VCH, Weinheim 1996, p. 619.
(eds.): Handbook of Heterogeneous Catalysis, 300 J. P. Arhancet, M. E. Davis, J. S. Merola, B. E.
Vol. 5, Wiley-VCH, Weinheim 1997, p. 2387. Hanson, Nature 339 (1989) 454;K. T. Wan, M. E.
279 F. Buonomo, D. Sanfilippo, F. Trifiro in G. Ertl, Davis, Nature 370 (1994) 449.
H. Kn€ozinger, J. Weitkamp (eds.): Handbook of 301 J. Adlkofer in G. Ertl, H. Kn€
ozinger, J. Weitkamp
Heterogeneous Catalysis, Vol. 5, Wiley-VCH, (eds.): Handbook of Heterogeneous Catalysis,
Weinheim 1997, p. 2140. Vol. 4, Wiley-VCH, Weinheim 1997, p. 1774.
280 S. H. Overbury, P. A. Bertrand, G. A. Somorja, 302 A. Riisager, P. Wasserscheid, R. van Hal, R.
Chem. Rev. 75 (1975) 547. Fehrmann, J. Catal. 219 (2003) 452.
281 Y. Ono, T. Baba: Catalysis, Vol. 15, The Royal 303 A. Riisager, R. Fehrmann, M. Haumann, P.
Society of Chemistry, Cambridge 2000, p. 1. Wasserscheid, Top. Catal. 40 (2006) 91.
282 K. Tanabe, H. Hattori in G. Ertl, H. Kn€ozinger, J. 304 U. Kernchen, B. Etzold, W. Korth, A. Jess,
Weitkamp (eds.): Handbook of Heterogeneous Chem. Eng. Technol. 30 (2007) 985.
Catalysis, Vol. 1, Wiley-VCH, Weinheim 1997, 305 G. Schulz-Ekloff, S. Ernst in G. Ertl, H. Kn€ ozin-
p. 404. ger, J. Weitkamp (eds.): Handbook of Heteroge-
283 X. Song, A. Sayari, Catal. Rev.-Sci. Eng. 38 neous Catalysis, Vol. 1, Wiley-VCH, Weinheim
(1996) 329. 1997, p. 374.
284 Topics in Catalysis 6 (1998). 306 D. E. De Vos, P. P. Knops-Gerrits, R. F. Parton, B.
285 K. Foger in J. R. Anderson, M. Boudart (eds.): M. Weckhuysen, P. A. Jacobs, R. A. Schoon-
Catalysis: Science and Technology, Vol. 6, heydt, J. Incl. Phnom. 21 (1995) 185.
Springer, Berlin 1984, p. 228. 307 R. Parton, D. E. De Vos, P. A. Jacobs in E. G.
286 B. C. Gates in G. Ertl, H. Kn€ozinger, J. Weitkamp Derouane, F. Lemos, C. Naccache, F. Ramoa
(eds.): Handbook of Heterogeneous Catalysis, Ribeiro (eds.): Zeolite Microporous Solids: Syn-
Vol. 2, Wiley-VCH, Weinheim 1997, p. 793. thesis, Structure and Reactivity, Kluwer Aca-
287 B. C. Gates, Chem. Rev. 95 (1995) 511. demic Publ., Dordrecht 1995, p. 555.
288 J. H. Sinfelt: Bimetallic Catalysts, Wiley, New 308 J.-M. Lehn: Supramolecular Chemistry, VCH
York 1983. Verlagsgesellschaft, Weinheim 1995.
289 C. T. Campbell in G. Ertl, H. Kn€ozinger, J. 309 M. P. McDaniel in G. Ertl, H. Kn€ ozinger, J.
Weitkamp (eds.): Handbook of Heterogeneous Weitkamp (eds.): Handbook of Heterogeneous
Catalysis, Vol. 2, Wiley-VCH, Weinheim Catalysis, Vol. 5, Wiley-VCH, Weinheim 1997,
1997, p. 814. p. 2400.
290 A. Baiker, Curr. Opin. Sol. State Mater. Sci. 3 310 W. Kaminsky, Adv. Catal. 46 (2001) 89.
(1998) 86. 311 W. Kaminsky, Macromol. Chem. Phys. 197
291 J. Wei in G. Ertl, H. Kn€ozinger, J. Weitkamp (1996) 3907.
(eds.): Handbook of Heterogeneous Catalysis, 312 S. Roy, T. Bauer, M. Al-Dahhan, P. Lehner, T.
Vol. 4, Wiley-VCH, Weinheim 1997, p. 1928. Turek, AIChE J. 50 (2004) 2918.
292 S. Helveg, J. V. Lauritsen, E. Lægsgaard, I. Stens- 313 I. Nova, A. Beretta, G. Groppi, L. Lietti, E.
gaard, J. K. Nørskov, B. S. Clausen, H. Topsøe, F. Tronconi, P. Forzatti in A. Cybulski, J. A. Mou-
Besenbacher, Phys. Rev. Lett. 84 (2000) 951. lijn (eds.)Structured Catalysts and Reactors,
293 D. E. De Vos, I. F. J. Vankelecom, P. A. Jacobs: 2nd ed., Taylor & Francis, Boca Raton 2006.
Chiral Catalyst Immobilization and Recycling, 314 K. Pangarkar, T. J. Schildhauer, J. R. van Om-
Wiley-VCH, Weinheim 2000. men, J. Nihenhuis, F. Kapteijn, J. A. Moulijn,
294 D. E. De Vos, S. de Wildman, B. F. Sels, P. J. Ind. Eng. Chem. Res. 47 (2008) 3720.
Grobet, P. A. Jacobs, Angew. Chem. 111 (1999) 315 M. V. Twigg, J. T. Richardson, Ind. Eng. Chem.
1033;Angew. Chem. Int. Ed. 38 (1999) 980. Res. 46 (2007) 4166.
295 K. Dranz, H. Waldmann: Enzyme Catalysis in 316 Y. Melatov-Meytal, M. Sheintuch, Appl. Catal.
Organic Synthesis, VCH Verlagsgesellschaft, A: General 231 (2002) 1.
Weinheim 1994. 317 B. A. A. L. van Setten, M. Makee, J. A. Moulijn,
296 A. W. Bosman, H. M. Janssen, E. W. Meijer, Catal. Rev. Sci. Eng. 43 (2001) 489.
Chem. Rev. 99 (1999) 1665. 318 V. Mehta, J. S. Cooper, J. Power Sources 114
297 H. Brunner, J. Organomet. Chem. 500 (1995) 39. (2003) 32.
298 A. Kirschning, H. Monenschein, R. Wittenberg, 319 E. Klemm, H. D€ oring, A. Geisselmann, S. Schirr-
Angew. Chem. Int. Ed. 40 (2001) 650. meister, Chem. Eng. Technol. 30 (2007) 1615.
104 Heterogeneous Catalysis and Solid Catalysts
320 K. Kochloefl, Quo vadis heterogene Katalyse, 339 D. H€ onicke, E. Dietzsch in F. Sch€ uth, K. S. W.
Dechema Tagung, XXVI Jahrestreffen Sing, J. Weitkamp (eds.): Handbook of Porous
deutscher Katalytiker, Schloß Reinhardsbrunn, Solids, Vol. 3, Wiley-VCH, Weinheim 2002,
Germany, 1993. p. 1395.
321 H. Heinemann: “Development of Industrial Cat- 340 T. A. Nijhuis, A. E. W. Beers, T. Vergunst, I.
alysis” in G. Ertl, H. Kn€ozinger, J. Weitkamp Hoek, F. Kapteijn, J. A. Moulijn, Catal. Rev. Sci.
(eds.): Handbook of Heterogeneous Catalysis, Eng. 43 (2001) 345.
Vol. 1, Wiley-VCH, Weinheim 1997, p. 35. 341 G. Ertl, H. Kn€ozinger, J. Weitkamp (eds.): Hand-
322 J. T. Richardson in M. V. Twigg, M. S. Spencer book of Heterogeneous Catalysis, Vol. 2, Wiley-
(eds.): Principle of Catalyst Development, Ple- VCH, Weinheim 1997.
num Press, New York 1989, p. 95. 342 K. S. W. Sing, D. H. Everett, R. A. W. Haul, L.
323 J. A. Cusumano in J. M. Thomas, K. I. Zamaraev Moscou, R. A. Pierotti, J. Rouquerol, T. Siemie-
(eds.): Perspectives in Catalysis, Blackwell niewska, Pure Appl. Chem. 57 (1985) 603.
Scient. Publ., Oxford 1991, p. 1. 343 K. S. W. Sing, J. Rouquerol in G. Ertl, H.
324 K. Fouhy, G. Samdani, S. Moore, Chem. Eng., Kn€ ozinger, J. Weitkamp (eds.): Handbook of
October (1992) 47. Heterogeneous Catalysis, Vol. 1, Wiley-VCH,
325 J. M. Fulton, Chem. Eng. 7 (1986) 59. Weinheim 1997, p. 427.
326 P. Courty, C. Marcilly in G. Poncelet, P. Grange, 344 J. Rouquerol, D. Avnir, C. W. Fairbridge, D. H.
P. Jacobs (eds.): Preparation of Catalysts III, Everett, J. M. Haynes, N. Pernicone, J. D. F.
Elsevier, Amsterdam 1983, p. 485. Ramsay, K. S. W. Sing, K. K. Unger, Pure Appl.
327 M. Sitting: Handbook of Catalyst Manufacture, Chem. 66 (1994) 1739.
Noyes Data Corp., Park Ridge 1971. 345 B. C. Lippens, J. H. de Boer, J. Catal. 4 (1965)
328 B. Stiles, T. A Koch, Catalyst Manufacture, 2nd. 319.
ed., M. Dekker, NewYork 1995. 346 K. S. W. Sing, D. H. Everett, R. H. Ottewill
329 F. Sch€uth, K. Unger in G. Ertl, H. Kn€ozinger, J. (eds.): Surface Area Determination, Butter-
Weitkamp (eds.): Handbook of Heterogeneous worths, London 1970, p. 25.
Catalysis, Vol. 1, Wiley-VCH, Weinheim 1997, 347 K. Datye in G. Ertl, H. Kn€ ozinger, J. Weitkamp
p. 72. (eds.): Handbook of Heterogeneous Catalysis,
330 E. I. Ko in G. Ertl, H. Kn€ozinger, J. Weitkamp Vol. 2, Wiley-VCH, Weinheim 1997, p. 493.
(eds.): Handbook of Heterogeneous Catalysis, 348 G. Bergeret, P. Gallezot in G. Ertl, H. Kn€
ozinger,
Vol. 1, Wiley-VCH, Weinheim 1997, p. 86. J. Weitkamp (eds.): Handbook of Heterogeneous
331 H. Jacobsen, P. Kleinschmit in G. Ertl, H. Catalysis, Vol. 2, Wiley-VCH, Weinheim 1997,
Kn€ozinger, J. Weitkamp (eds.): Handbook of p. 439.
Heterogeneous Catalysis, Vol. 1, Wiley-VCH, 349 P. Gallezot in J. R. Anderson, M. Boudart (eds.):
Weinheim 1997, p. 94. Catalysis: Science and Technology, Vol. 5,
332 J. W. Geus, J. van Dillen: “Preparation of Sup- Springer, Berlin 1984, p. 221.
ported Catalysts by Deposition – Precipitation” 350 R. J. Matyi, L. R. Schwartz, J. B. Butt, Catal.
in G. Ertl, H. Kn€ ozinger, J. Weitkamp (eds.): Rev.-Sci. Eng. 29 (1987) 41.
Handbook of Heterogeneous Catalysis, Vol. 1, 351 A. K. Datye, D. J. Smith, Catal. Rev.-Sci. Eng. 34
Wiley-VCH, Weinheim 1997, p. 240. (1992) 129.
333 E. J. P. Feijen, J. A. Martens, P. A. Jacobs in G. 352 H. Poppa, Catal. Rev.-Sci. Eng. 35 (1993) 359.
Ertl, H. Kn€ozinger, J. Weitkamp (eds.): Hand- 353 M. J. Yacaman, G. Diaz, A. Gomez, Catal. Today
book of Heterogeneous Catalysis, Vol. 1, Wiley- 23 (1995) 161.
VCH, Weinheim 1997, p. 311. 354 G. Bergeret in G. Ertl, H. Kn€
ozinger, J. Weitkamp
334 J. Barbier in G. Ertl, H. Kn€ozinger, J. Weitkamp (eds.): Handbook of Heterogeneous Catalysis,
(eds.): Handbook of Heterogeneous Catalysis, Vol. 2, Wiley-VCH, Weinheim 1997, p. 464.
Vol. 1, Wiley-VCH, Weinheim 1997, p. 257. 355 B. S. Clausen, G. Steffensen, B. Fabius, J.
335 J. F. Le Page in G. Ertl, H. Kn€ozinger, J. Villadsen, L. R. Feidenhaus, H. Topsøe, J. Catal.
Weitkamp (eds.): Handbook of Heterogeneous 132 (1991) 524.
Catalysis, Vol. 1, Wiley-VCH, Weinheim 356 M. Vaarkamp, D. C. Konigsberger in G. Ertl, H.
1997, p. 412. Kn€ ozinger, J. Weitkamp (eds.): Handbook of
336 J. W. Fulton, Chem Eng.,May 12 (1986) 97. Heterogeneous Catalysis, Vol. 2, Wiley-VCH,
337 General Catalogue, S€ud-Chemie AG, Catalyst Weinheim 1997, p. 475.
Division, Munich Germany. 357 J. H. Sinfelt, G. D. Meitzner, Acc. Chem. Res. 26
338 V. Meille, Appl. Catal. A: General 315 (2006) 1. (1993) 1.
Heterogeneous Catalysis and Solid Catalysts 105
402 D. A. M. Monti, A. Baiker, J. Catal. 83 (1983) 427 M. Hunger, Solid State Nucl. Magn. Res. 6
323. (1996) 1.
403 P. Malet, A. Caballero, J. Chem. Soc. Faraday 428 V. Bosacek, J. Phys. Chem. 97 (1993) 10732;
Trans. I 84 (1988) 2369. andZ. Phys. Chem. 189 (1995) 241.
404 V. B. Kazansky in G. Ertl, H. Kn€ozinger, J. Weit- 429 J. F. Le Page: Applied Heterogeneous Catalysis
kamp (eds.): Handbook of Heterogeneous Catal- Design, Manufacture, Use of Solid Catalysts,
ysis, Vol. 2, Wiley-VCH, Weinheim 1997, p. 740. Editions Technip, Paris 1987.
405 W. K. Hall in G. Ertl, H. Kn€ozinger, J. Weitkamp 430 J. C. Dart, Chem. Eng. Prog. 71 (1975) 46; andE.
(eds.): Handbook of Heterogeneous Catalysis, R. Beaver, Chem. Eng. Prog. 71 (1975) 44.
Vol. 2, Wiley-VCH, Weinheim 1997, p. 692. 431 W. L. Forsythe, W. R. Hertwig, Ind. Eng. Chem.
406 H. A. Benesi, J. Phys. Chem. 61 (1957) 970. 41 (1949) 1200.
407 M. Deeba, W. K. Hall, J. Catal. 60 (1979) 417. 432 C. O. Bennett, Adv. Catal. 44 (1999) 329.
408 B. E. Spiewak, R. D. Cartright, J. A. Dumesic in 433 K. Tamaru in J. R. Anderson, M. Boudart (eds.):
G. Ertl, H. Kn€ozinger, J. Weitkamp (eds.): Hand- Catalysis: Science and Technology, Vol. 9,
book of Heterogeneous Catalysis, Vol. 2, Wiley- Springer, Berlin, 1991, p. 87.
VCH, Weinheim 1997, p. 698. 434 J. T. Gleaves, J. R. Ebner, T. C. Kuechler, Catal.
409 J. L. Falconer, J. A. Schwarz, Catal. Rev.-Sci. Rev.-Sci. Eng. 30 (1988) 49.
Eng. 25 (1983) 414. 435 O. V. Buyevskaya, M. Rothaemel, H. W. Zanth-
410 H. Karge, V. Dondur, J. Phys. Chem. 94 (1990) off, M. Baerns, J. Catal. 150 (1994) 71.
765. 436 G. Creten, D. S. Lafyatis, G. F. Froment, J.
411 S. Chatterjee, H. L. Greene, Y. J. Park, J. Catal. Catal. 154 (1995) 151.
138 (1992) 179. 437 S. L. Shannon, J. G. Goodwin, Jr., Chem. Rev. 95
412 A. Auroux, A. Gervasini, J. Phys. Chem. 94 (1995) 677.
(1990) 6371. 438 A. Ozaki: Isotopic Studies of Heterogeneous
413 D. T. Chen, L. Zhang, C. Yi, J. A. Dumesic, J. Catalysis, Kodansha, Tokyo and Academic
Catal. 146 (1994) 257. Press, New York, 1977.
414 W. E. Farneth, R. J. Gorte, Chem. Rev. 95 (1995) 439 G. F. Berndt in Catalysis, Vol. 6, The Royal
615. Society of Chemistry, London, 1983, p. 144.
415 H. Kn€ozinger in G. Ertl, H. Kn€ozinger, J. Weit- 440 G. Liu, D. Willcox, M. Garland, H. H. Kung, J.
kamp (eds.): Handbook of Heterogeneous Catal- Catal. 96 (1985) 251.
ysis, Vol. 2, Wiley-VCH, Weinheim 1997, p. 707. 441 R. P. Bell, Chem. Soc. Rev. 3 (1974) 513.
416 E. A. Paukshtis, E. N. Yurchenko, Russ. Chem. 442 L. Melander, W. H. Sauder, Jr., Reaction Rates of
Rev. 52 (1983) 42. Isotopic Molecules, Wiley, New York 1980.
417 J. C. Lavalley, Trends Phys. Chem. 2 (1991) 305. 443 S. Siegel, Adv. Catal. 16 (1966) 124.
418 J. A. Lercher, C. Gr€undling, G. Eder-Mirth, 444 M. Kraus, Adv. Catal. 29 (1980) 151.
Catal. Today 27 (1996) 353. 445 M. Kraus in G. Ertl, H. Kn€ ozinger, J. Weitkamp
419 J. C. Lavalley, Catal. Today 27 (1996) 377. (eds.): Handbook of Heterogeneous Catalysis,
420 H. Kn€ozinger, S. Huber, J. Chem. Soc. Faraday Vol. 3, Wiley-VCH, Weinheim 1997, p. 1051.
Trans. 94 (1998) 2047. 446 H. Kn€ ozinger, Adv. Catal. 25 (1976) 184.
421 G. C. Pimentel, A. L. McClellan: The Hydrogen 447 C. Appel, J. Mantzaras, R. Schaeren, R. Bom-
Bond, Freeman, San Francisco, London 1960. bach, A. Inauen, Combust. Flame, 140 (2005)
422 S. Huber, H. Kn€ozinger, J. Mol. Catal. 141 70.
(1999) 117. 448 T. Horstmann, H. Leuckel, B. Maurer, U. Maas,
423 A. M. Ferrari, S. Huber, H. Kn€ozinger, K. M. Proc. Safety Progr. 20 (2001) 215.
Neyman, N. R€osch, J. Phys. Chem. B 102 (1998) 449 H. P. A. Calis, J. Nijenhuis, B. C. Paikert, F. M.
4548. Dautzenberg, C. M. van den Bleek, Chem. Eng.
424 H. Kn€ozinger, H. Krietenbrink, H. D. M€uller, W. Sci. 56 (2001) 1713.
Schulz: Proceedings of the 6th International 450 C. Appel, J. Mantzaras, R. Schaeren, R. Bom-
Congress on Catalysis, London, 1976, The bach, B. Kaeppeli, A. Inauen, Proc. Combust.
Chemical Society, London 1977, p. 183. Inst. 29 (2003) 1031.
425 H. Pfeifer in G. Ertl, H. Kn€ozinger, J. Weitkamp 451 M. Reinke, J. Mantzaras, R. Schaeren, R. Bom-
(eds.): Handbook of Heterogeneous Catalysis, bach, W. Kreutner, A. Inauen, Proc. Combust.
Vol. 2, Wiley-VCH, Weinheim 1997, p. 732. Inst. 29 (2002) 1021.
426 V. M. Mastikhin, I. L. Mundrakovsky, A. V. 452 U. Dogwiler, P. Benz, J. Mantzaras, Combust.
Nosov, Progress NMR Spectrosc. 23 (1991) 259. Flame 116 (1999) 243.
Heterogeneous Catalysis and Solid Catalysts 107
453 M. Reinke, J. Mantzaras, R. Schaeren, R. Bom- 478 K. R. Westerterp, Chem. Eng. Sci. 47 (1992) 2195.
bach, A. Inauen, S. Schenker, Combust. Flame 479 J. Werther, H. Schoenfelder in G. Ertl, H.
136 (2004) 217. Kn€ ozinger, J. Weitkamp (eds.): Handbook of
454 U. Kunz, U. Peuker, T. Turek, M. Estenfelder in Heterogeneous Catalysis, Vol. 3, Wiley-VCH,
U. Br€ockel, W. Meier, G. Wagner (eds.): Product Weinheim 1997, p. 1426.
Design and Engineering, Wiley-VCH, Wein- 480 D. Geldart (ed.): Gas Fluidization Technology,
heim 2007. Wiley, Chichester 1986.
455 C. N. Satterfield, T. K. Sherwood: Role of Dif- 481 J. F. Davidson, R. Clift, D. Harrison: Fluidiza-
fusion in Catalysis, Addison-Wesley, Reading, tion, Academic Press, London 1985.
Mass. 1963, p. 56. 482 M. Pell: Gas Fluidization, Elsevier, Amsterdam
456 C. N. Satterfield: Mass Transfer in Heteroge- 1990.
neous Catalysis, MIT Press, Cambridge, Mass., 483 A. A. C. M. Beenackers in G. Ertl, H. Kn€
ozinger, J.
1970, p. 129. Weitkamp (eds.): Handbook of Heterogeneous
457 E. W. Thiele, Ind. Eng. Chem. 31 (1939) 916. Catalysis, Vol. 3, Wiley-VCH, Weinheim 1997,
458 G. Damk€ohler, Chem. Ing. 3 (1939) 430. p. 1444.
459 Y. B. Zeldowitch, Acta Physicochim. USSR 10 484 L. K. Doraiswamy, M. M. Sharma: Heterogeneous
(1939) 582. Reactions, Vol. 2, Wiley, New York 1984, p. 9.
460 P. B. Weisz, Adv. Catal. 13 (1962) 137. 485 B. Jager, R. Espinoza, Catal. Today 23 (1995) 17.
461 C. D. Prater, Chem. Eng. Sci. 8 (1958) 284. 486 W. Ehrfeld, V. Hessel, H. L€ owe: Microreactors,
462 P. B. Weisz, C. D. Prater, Adv. Catal. 6 (1954) 143. Wiley-VCH, Weinheim 2000.
463 E. Wicke, Angew. Chem. 19 (1947) 57. 487 K.-F. Jensen, Chem. Eng. Sci. 56 (2001) 293.
464 E. Wicke, Z. Elektrochem. 60 (1956) 774. 488 S. J. Haswell, R. J. Middleton, B. O’Sullivan, V.
465 R. Aris: The Mathematical Theory of Diffusion Skelton, P. Watts, P. Styring, J. Chem. Soc.
and Reaction in Permeable Catalysts,Vols. 1 Chem. Commun. 2001, 391.
and 2, Clarendon Press, Oxford 1975. 489 T. Wirth (ed.): Microreactors in Organic Syn-
466 J. J. Carberry in J. R. Anderson, M. Boudart thesis and Catalysis, Wiley-VCH, Weinheim
(eds.): Catalysis — Science and Technology, 2008.
Vol. 8, Springer, Berlin 1987, p. 131. 490 K. J€ahnisch, V. Hessel, H. L€ owe, M. Baerns,
467 P. B. Weisz, J. S. Hicks, Chem. Eng. Sci. 17 Angew. Chem. Int. Ed. 43 (2004) 406.
(1962) 265. 491 L. Kiwi-Minsker, A. Renken, Catal. Today 110
468 A. Wheeler, Adv. Catal. 2 (1951) 250. (2005) 2.
469 F. Kapteijn, J. A. Moulijn in G. Ertl, H. Kn€ozinger, 492 G. Veser, Chem. Eng. Sci. 56 (2001) 1265.
J. Weitkamp (eds.): Handbook of Heterogeneous 493 T. Inoue, M. A. Schmidt, K. F. Jensen, Ind. Eng.
Catalysis, Vol. 3, Wiley-VCH, Weinheim 1997, Chem. Res. 46 (2007) 1153.
p. 1359. 494 P. D. I. Fletcher, S. J. Haswell, Chem. Br. 35
470 K. C. Pratt in J. R. Anderson, M. Boudart (eds.): (1999) 38.
Catalysis — Science and Technology, Vol. 8, 495 E. Klemm, E. Dietzsch, T. Schwarz, T. Kruppa,
Springer, Berlin 1987, p. 173. A. L. de Oliveira, F. Becker, G. Markowz, S.
471 R. J. Farrauto, C. H. Bartholomew: Fundamen- Schirrmeister, R. Sch€ utte, K. J. Caspary, F.
tals of Industrial Catalytic Processes, Blackie Sch€ uth, D. H€onicke, Ind. Eng. Chem. Res. 47
Academic & Professional, London 1997, p. 199. (2008) 2086.
472 J. M. Berty, Plant Oper. Progr. 3 (1984) 163. 496 Y. Sh. Matros, G. A. Bunimovich in G. Ertl, H.
473 L. K. Doraiswamy, D. G. Tjabl, Cat. Rev.-Sci. Kn€ ozinger, J. Weitkamp (eds.): Handbook of
Eng. 10 (1974) 177. Heterogeneous Catalysis, Vol. 3, Wiley-VCH,
474 J. Weitkamp in G. Ertl, H. Kn€ozinger, J. Weitkamp Weinheim 1997, p. 1464.
(eds.): Handbook of Heterogeneous Catalysis, 497 A. Renken, Int. Chem. Eng. 33 (1993) 61.
Vol. 3, Wiley-VCH, Weinheim 1997, p. 1376. 498 J.-A. Dalmon in G. Ertl, H. Kn€ ozinger, J. Weit-
475 G. Eigenberger in G. Ertl, H. Kn€ozinger, J. Weit- kamp (eds.): Handbook of Heterogeneous Cataly-
kamp (eds.): Handbook of Heterogeneous Cataly- sis, Vol. 3, Wiley-VCH, Weinheim 1997, p. 1387.
sis, Vol. 3, Wiley-VCH, Weinheim 1997, p. 1399. 499 H. P. Hsieh, Catal. Rev.-Sci. Eng. 33 (1991) 1.
476 G. F. Froment, K. B. Bischoff: Chemical Reactor 500 G. Sarraco, V. Specchia, Catal. Rev.-Sci. Eng. 36
Analysis and Design, Wiley, New York 1990. (1994) 305.
477 K. R. Westerterp, W. P. M. van Swaaj, A. A. C. 501 R. Soria, Catal. Today 25 (1995) 285.
M. Beenackers: Chemical Reactor Design and 502 G. Donati, N. Habashi, I. Miracca, D. Sanfilippo
Operation, Wiley, New York 1984. in G. Ertl, H. Kn€ ozinger, J. Weitkamp (eds.):
108 Heterogeneous Catalysis and Solid Catalysts
Handbook of Heterogeneous Catalysis, Vol. 3, 525 M. Nijemeisland, A. G. Dixon, Am. Inst. Chem.
Wiley-VCH, Weinheim 1997, p. 1479. Eng. J. 2004, 50 () 906.
503 D. B. Keyes, Ind. Eng. Chem. 24 (1932) 1096. 526 T. Zeiser, P. Lammers, E. Klemm, Y. W. Li, J.
504 D. F. Othmer, Ind. Eng. Chem. 33 (1941) 1106. Bernsdorf, G. Brenner, Chem. Eng. Sci. 56
505 P. E. Sauvage in G. Ertl, H. Kn€ozinger, J. Weit- (2001) 1697.
kamp (eds.): Handbook of Heterogeneous Ca- 527 J. Neumann, H. Golitzer, A. Heywood, I. Ticu,
talysis, Vol. 3, Wiley-VCH, Weinheim 1997, Revista Chim. 53 (2002) 721.
p. 1339. 528 R. Quiceno, J. Perez-Ramırez, J. Warnatz, O.
506 A. Baiker, Chem. Rev. 99 (1999) 453. Deutschmann, Appl. Catal. A 303 (2006) 166.
507 P. G. Jessop, W. Leitner (eds.): Chemical Syn- 529 D. L. Trimm in G. Ertl, H. Kn€ ozinger, J. Weit-
thesis Using Supercritical Fluids, Wiley-VCH, kamp (eds.): Handbook of Heterogeneous Ca-
Weinheim 1999. talysis, Vol. 3, Wiley-VCH, Weinheim 1997,
508 R. Wandeler, A. Baiker, Cattech 4 (2000) 128. p. 1263.
509 R. J. Kee, F. M. Rupley, J. A. Miller, M. E. 530 J. R. Rostrup-Nielsen in C. H. Bartholomew, J.
Coltrin, J. F. Grcar, E. Meeks, H. K. Moffat, A. E. B. Butt (eds.): Catalyst Deactivation, Elsevier
Lutz, G. Dixon-Lewis, M. D. Smooke, J. War- Science, Amsterdam 1991.
natz, G. H. Evans, R. S. Larson, R. E. Mitchell, 531 J. Barbier in J. Oudar, H. Wise (eds.): Deactiva-
L. R. Petzold, W. C. Reynolds, M. Caracotsios, tion and Poisoning of Catalysts, M. Dekker, New
W. E. Stewart, P. Glarborg, C. Wang, O. Adigun, York 1985.
CHEMKIN, 3.6 ed., Reaction Design, Inc., 532 C. H. Bartholomew, P. K. Agrawal, J. R. Katzer,
www.chemkin.com, San Diego, 2000. Adv. Catal. 31 (1982) 135.
510 D. G. Goodwin,CANTERA. An open-source, 533 P. Dufresne, A. Quesada, S. Miguarel in D. L.
extensible software suite for CVD process sim- Trimm, S. Akasheh, M. Absi-Halabi, A. Bishara
ulation, www.cantera.org, 2003. (eds.): Catalysis in Petroleum Refining, Elsevier
511 O. Deutschmann, S. Tischer, C. Correa, D. Science, Amsterdam 1990.
Chatterjee, S. Kleditzsch, V. M. Janardhanan, 534 K. Tanabe, M. Misono, Y. Ono, H. Hattori: New
DETCHEM software package, 2.0 ed., www. Solid Acids and Bases, Elsevier, Amsterdam
detchem.com, Karlsruhe, 2004. 1989.
512 Fluent, Fluent Incorporated, www.fluent.com, 535 D. L. Trimm, Chem. Eng. Process 18 (1984) 137.
Lebanon, NH, 2005. 536 D. C. McCulloch in B. Leach (ed.): Applied
513 CD-adapco, London Office, 200 Shepherds Industrial Catalysis, Vol. 1, Academic Press,
Bush Road, London, W6 7NY, United Kingdom, New York 1983, p. 103.
www.cd-adapco.com. 537 Y. Huang, N. W. Cant, J. Guerbios, D. L. Trimm,
514 FIRE, AVL LIST GmbH, www.avl.com, Graz, A. Walpole: Proc. Third Intern. Congress on
Austria, 2005. Catal. and Automotive Pollution Control, Brus-
515 CFD-ACþ, CFD Research Corporation, www. sels, Elsevier, Amsterdam 1995, p. 56.
cfdrc.com, Huntsville, AL, 2005. 538 C. A. Bernardo, D. L. Trimm, Carbon 17 (1979)
516 CFX, www-waterloo.ansys.com, 2005. 115.
517 J. Shadid, S. Hutchinson, G. Hennigan, H. Mof- 539 H. Hiller et al.: “Gas Production”, in Ullmann’s
fat, K. Devine, A. G. Salinger, Parallel Comput. Encyclopedia of Industrial Chemistry, Vol. A12,
23 (1997) 1307. Wiley-VCH, Weinheim 2006.
518 L. L. Raja, R. J. Kee, O. Deutschmann, J. War- 540 P. H€aussinger, R. Lohm€ uller, A. M. Watson:
natz, L. D. Schmidt, Catal. Today 59 (2000) 47. “Hydrogen”, in Ullmann’s Encyclopedia of In-
519 J. Mantzaras, C. Appel, P. Benz, U. Dogwiler, dustrial Chemistry, Vol. A13, Wiley-VCH,
Catal. Today 59 (2000) 3. Weinheim 2002, p. 189.
520 R. Jahn, D. Snita, M. Kubicek, M. Marek, Catal. 541 S. Ernst, W. Petzny in R. Dittmeyer, W. Keim, G.
Today 38 (1997) 39. Kreysa, A. Oberholz (eds.): Winnacker-K€ uchler,
521 G. C. Koltsakis, P. A. Konstantinidis, A. M. 5. ed, Vol. 4, Wiley-VCH, Weinheim 2005,
Stamatelos, Appl. Catal. B 12 (1997) 161. p. 523.
522 S. Tischer, C. Correa, O. Deutschmann, Catal. 542 J. R. Rostrup-Nielsen in G. Ertl, H. Kn€
ozinger, F.
Today 69 (2001) 57. Sch€uth, J. Weitkamp (eds.): Handbook of Het-
523 S. Tischer, O. Deutschmann, Catal. Today 105 erogeneous Catalysis, 2nd ed., Vol. 6, Wiley-
(2005) 407. VCH, Weinheim 2008, p. 2882.
524 R. Schwiedernoch, S. Tischer, C. Correa, O. 543 J. R. Rostrup-Nielsen, J. Sehested, J. K. Nors-
Deutschmann, Chem. Eng. Sci. 58 (2003) 633. kov.Adv. Catal. 47 (2002) 65.
Heterogeneous Catalysis and Solid Catalysts 109
544 J. Wei, E. Iglesia, J. Phys. Chem. B 108 (2004) 567 H. Topsøe, N. Topsøe, Top. Catal. 8 (1999) 267.
4094. 568 T. S. Askgaard, J. K. Norskov, C. V. Ovesen, P.
545 D. A. Hickman, L. D. Schmidt, J. Catal. 138 Stoltze, J. Catal. 156 (1995) 229.
(1992) 267. 569 K. M. Vanden Bussche, G. F. Froment, J. Catal.
546 J. J. Krummenacher, K. N. West, L. D. Schmidt, 161 (1996) 1.
J. Catal. 215 (2003) 332. 570 B. Lommerts, G. Graff, A. Beenackers, Chem.
547 J. R. Salge, G. A. Deluga, L. D. Schmidt, J. Eng. Sci. 55 (2000) 5589.
Catal. 235 (2005) 69. 571 R. G. Herman in L. Guczi (ed.): New Trends in
548 J. N. Armor, J. Membrane Sci. 147 (1998) 217. CO Activation, Elsevier, New York 1991.
549 I. Aartun, B. Silberova, H. Venvik, P. Pfeifer, O. 572 F. Fischer, H. Tropsch, Brennst. Chem. 4 (1923)
Gorke, K. Schubert, A. Holmen, Catal. Today 276.
105 (2005) 469. 573 R. B. Anderson in P. H. Emmett (ed.): Catalysis,
550 T. J. Remans, G. Jenzer, A. Hoek in G. Ertl, H. Vol. 4, Van Nostrand-Rheinhold, New York 1956.
Kn€ozinger, F. Sch€uth, J. Weitkamp (eds.): Hand- 574 A. T. Bell, Catal. Rev. Sci. Eng. 23 (1981) 203.
book of Heterogeneous Catalysis, 2nd ed., Vol. 575 G. P. van der Laan, A. A. C. M. Beenackers,
6, Wiley-VCH, Weinheim 2008, p. 2994. Catal. Rev. Sci. Eng. 41 (1999) 255.
551 G. A Olah, A. Goeppert, G. K. S. Prakash: 576 T. Riedel,PhD thesis, Universit€at Karlsruhe
Beyond Oil and Gas: The Methanol Economy, (TH), Karlsruhe2002.
Wiley-VCH, Weinheim 2006. 577 B. H. Davis, Top. Catal. 32 (2005) 143.
552 D. C. Rennard, P. J. Dauenhauer, S. A. Tupy, L. 578 R. Oukaci, A. H. Singleton, J. G. Goodwin, Jr.,
D. Schmidt, Energy Fuels 22 (2008) 1318. Appl. Catal. A 186 (1999) 129.
553 P. J. Dauenhauer, B. J. Dreyer, N. J. Degenstein, 579 M. E. Dry, J. Mol. Catal. 17 (1982) 133.
L. D. Schmidt, Angew. Chem. Int. Ed. 46 (2007) 580 S. T. Sie, Rev. Chem. Eng. 14 (1988) 109.
5864. 581 F. G. Botes, W. B€ ohringer, Appl. Catal A: Gen-
554 E. C. Wanat, B. Suman, L. D. Schmidt, J. Catal. eral 267 (2004) 217.
235 (2005) 18. 582 A. M. Subiranas, G. Schaub, Int. J. Chem. React.
555 K.-O. Hinrichsen, K. Kochloefl, M. Muhler in G. Eng. 5 (2007) A78.
Ertl, H. Kn€ozinger, F. Sch€uth, J. Weitkamp (eds.): 583 M. F. M. Post, A. C. van’t Hoog, J. K. Mind-
Handbook of Heterogeneous Catalysis, 2nd ed., erhoug, S. T. Sie, AIChE J. 35 (1989) 1107.
Vol. 6, Wiley-VCH, Weinheim 2008, p. 2905. 584 Y.-N. Wang, Y.-Y. Xu, H.-W. Xiang, Y.-W. Li, B.
556 D. S. Newsome, Catal. Rev. Sci. Eng. 21 (1980) J. Zhang, Ind. Eng. Chem. Res. 40 (2001) 4324.
275. 585 A.-M. Hilmen, E. Bergene, O. A. Lindvag, D.
557 G. Ertl in J. R. Jennings (ed.): Catalytic Ammo- Schanke, S. Eri, A. Holmen, Catal. Today 69
nia Synthesis: Fundamentals and Practice, Fun- (2001) 227.
damental and Applied Catalysis, Plenum Press, 586 R. K. Grasselli in G. Ertl, H. Kn€ ozinger, J.
New York 1991, p. 109. Weitkamp (eds.): Handbook of Heterogeneous
558 R. Schl€ogel in G. Ertl, H. Kn€ozinger, F. Sch€uth, Catalysis, Vol. 5, Wiley-VCH, Weinheim 1997,
J. Weitkamp (eds.): Handbook of Heterogeneous p. 2302.
Catalysis, 2nd ed., Vol. 5, Wiley-VCH, Wein- 587 R. A. van Santen G. Ertl, H. Kn€ ozinger, J. Weit-
heim 2008, p. 2501. kamp (eds.): Handbook of Heterogeneous Catal-
559 K. Aika, A. Ozaki, J. Catal. 16 (1970) 97. ysis, Vol. 5, Wiley-VCH, Weinheim 1997,
560 F. Bozso, G. Ertl, M. Weiss, J. Catal. 50 (1977) p. 2244.
519. 588 R. A. van Santen, H. C. P. E. Kuipers, Adv. Catal.
561 P. H. Emmett, S. Brunauer, J. Am. Chem. Soc. 59 35 (1988) 265.
(1937) 310. 589 M. C. Zonnevylle, J. J. C. Geerlings, R. A. van
562 M. Boudart, Catal. Rev.-Sci. Eng. 23 (1981) 1. Santen, J. Catal. 148 (1994) 417.
563 G. Ertl, M. Weiss, S. B. Lee, Chem. Phys. Lett. 590 M. Neurock, R. A. van Santen, W. Biemolt, A. P.
60 (1979) 391. J. JansenJ. Am. Chem. Soc. 116 (1994) 6860.
564 M. Muhler, E. T€ornqvist, L. P. Nielsen, B. S. 591 J. W. He, U. Memmert, K. Griffiths, P. R. Norton,
Clausen, H. Topsøe, Catal. Lett. 25 (1994) 1. J. Chem. Phys. 90 (1989) 5082.
565 R. Burch, R. J. Chappell, S. E. Golunski, J. 592 P. J. van den Hoek, E. J. Baerends, R. A. van
Chem. Soc. Faraday Trans. 1 85 (1989) 3569. Santen, J. Phys. Chem. 93 (1989) 6469.
566 J. Nakamura, I. Nakamura, T. Uchima, T. Wa- 593 L. M. Akella, H. N. Lee, J. Catal. 86 (1984)
tanabe, T. Fujitani, Stud. Surf. Sci. Catal. 101 465.
(1996) 1389. 594 M. Bowker, R. C. Waugh, Surf. Sci. 155 (1984) 1.
110 Heterogeneous Catalysis and Solid Catalysts
595 P. Arpentinier, F. Cavani, F. Trifiro: The Tech- 615 US 4 085 193, 1978(F. Nakajima, M. Takeuchi,
nology of Catalytic Oxidations, Vol. 1, Editions S. Matsuda, S. Uno, T. Mori, Y. Watanabe, M.
Technip, Paris 2001, p. 245. Inamuri).
596 G. Bellussi, M. S. Rigutto, Stud. Surf. Sci. Catal. 616 C. Orsenigo, L. Lietti, E. Tronconi, P. Forzatti, F.
85 (1991) 177. Bregani, Ind. Eng. Chem. Res. 37 (1998) 2350.
597 M. G. Clerici, Oil Gas Eur. Mag. 32 (2006) 77. 617 G. S. Qi, R. T. Yang, R. Chang, S. Cardoso, R. A.
598 B. Ford, Chem. Market. Rep. 269 (2006) 24. Smith, Appl. Catal. A: General 275 (2005) 207.
599 P. N. Rylander in J. R. Anderson, M. Boudart 618 M. Groves, M. Schwefer, R. Siefert, TCE 778
(eds.): Catalysis: Science and Technology, (2006) 30.
Vol. 4, Springer, Berlin 1983, p. 1. 619 M. Votsmeier, T. Kreuzer, G. Lepperhoff:
600 J. F. Brazdil, Top. Catal. 38 (2006) 289. “Automobile Exhaust Control” in Ullmann’s
601 P. Mars, D. W. van Krevelen, Chem. Eng. Sci. Encyclopedia of Industrial Chemistry, Vol.
Special Suppl. 3 (1954) 41. A3, Wiley-VCH, Weinheim 2005, p. 189
602 R. K. Grasselli, J. D. Burrington, I & EC Res. & 620 S. J. Lox in G. Ertl, H. Kn€ ozinger, F. Sch€uth, J.
Dev. 23 (1984) 393. Weitkamp (eds.): Handbook of Heterogeneous
603 T. P. Snyder, C. G. Hill, Catal. Rev.-Sci. Eng. 31 Catalysis, 2nd ed., Vol. 5 Wiley-VCH, Wein-
(1989) 43. heim 2008, p. 2274.
604 J. D. Burrington, C. T. Kartisek, R. K. Grasselli, 621 R. M. Heck, R. J. Farrauto, S. T. Gulati, Catalytic
J. Catal. 87 (1984) 363. Air Pollution Control, Wiley-InterSci., New
605 J. M. Lopez Nieto, Top. Catal. 41 (2006) 3. York 2002.
606 B. C. Gates: Catalytic Chemistry, Wiley, New 622 S. Kureti,Habilitation thesis, Fakult€at f€ur Che-
York 1992, p. 406. mie und Biowissenschaften, Universit€at Karls-
607 R. Prius in G. Ertl, H. Kn€ozinger, J. Weitkamp ruhe (TH), 2008.
(eds.): Handbook of Heterogeneous Catalysis, 623 M. V. Twigg, Appl. Catal. B 70 (2007) 2.
Vol. 4, Wiley-VCH, Weinheim 1997, p. 1908. 624 D. Chatterjee, O. Deutschmann, J. Warnatz,
608 D. D. Whitehurst, T. Isoda, I. Mochida, Adv. Faraday Discuss. 119 (2001) 371.
Catal. 42 (1998) 345. 625 N. Fekete, R. Kemmler, D. Voigtl€ander, B.
609 M. Houalla, N. K. Nag, A. V. Sapre, D. H. Krutzsch, E. Room, G. Wenninger, W. Streh-
Broderick, B. C. Gates, AIChE J. 24 (1978) 1015. lau, J. A. A. van den Tillaart, J. Leyrer, E. S.
610 A. Kundu, K. D. P. Nigam, A. M. Duquenne, H. Lox, W. M€ uller, SAE Technical Paper 960133
Delmas, Rev. Chem. Eng. 6 (2003) 531. (1996)
611 M. S. Rana, V. Samano, J. Ancheyta, J. A. I. 626 F. Rohr, S. D. Peter, E. Lox, M. K€ogel, A. Sassi,
Diaz, Fuel 86 (2007) 1216. L. Juste, C. Rigaudeau, G. Belot, P. Gelin, M.
612 M. Koebel, M. Elsener, G. Madia, Ind. Eng. Primet, Appl. Catal. B 56 (2005) 201.
Chem. Res. 40 (2001) 52. 627 P. Zelenka, W. Cartellieri, P. Duke, Appl. Catal.
613 US 2 975 025, 1961(G. Cohn, D. Steele, H. B 7 (1996) 3.
Andersen). 628 O. Salvat, P. Marez, G. Belot, SAE Technical
614 US 3 279 884, 1966(K. Kartte, H. Nonnenmaker). Paper 2000-01-0473(2000).