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Monolithic reactors in catalysis: excellent control


Jacob A Moulijn and Freek Kapteijn

Structured reactors offer high precision in catalysis at all [3,5,6]. Microfabricated reactors belong also to the
relevant length scales of the catalytic process, from the family of structured reactors [7].
catalytic species up to the reactor. They offer unusual freedom
in design with respect to diffusion length, hydrodynamic regime In this perspective we emphasize monolith reactors,
and reactor configuration. Monoliths are the prime example of conceptually the simplest and most widespread.
such systems.
Monoliths
Addresses
Catalysis Engineering, ChemE, Delft University of Technology,
The name ‘monolith’ stems from the Greek mono and
Julianalaan 136, 2628 BL Delft, The Netherlands lithos, single and stone. In catalytic reaction engineering, a
monolith is defined as a single block of catalyst-contain-
Corresponding author: Moulijn, Jacob A (j.a.moulijn@tudelft.nl) ing material through which reactants and products are
transported by convection. It has such macroscopic
dimensions that one or a few monoliths can completely
Current Opinion in Chemical Engineering 2013, 2:346–353 fill the catalytic reactor space. In separation technology
This review comes from a themed issue on Reaction engineering and and in flow chemistry [8] reactor-filling rods with well-
catalysis defined macro- and mesoporosity are used, also referred
Edited by Marc-Olivier Coppens and Theodore T Tsotsis to as ‘monoliths’. These structures are not part of this
For a complete overview see the Issue and the Editorial review.
Available online 27th June 2013
Monoliths are characterized by channel shape, cell
2211-3398/$ – see front matter, # 2013 Elsevier Ltd. All rights
reserved.
density, and wall thickness [3,9]. For example, the
square 400 cpsi monolith, containing 400 cells per square
http://dx.doi.org/10.1016/j.coche.2013.05.003
inch with a wall thickness of typically 0.13 mm, is often
used in three-way catalysts for conversion of automobile
exhaust. Channel shapes are usually square, rectangular,
Introduction hexagonal, or triangular [10].
Fixed bed and slurry reactors are the workhorses in the
chemical industry and they share the benefits of simpli- The monolith is probably the most popular catalytic
city of construction on the upside and chaotic and hard-to- reactor of all. Why is it so popular? The large, open frontal
predict fluid mechanics on the downside. Instead of area giving access to straight channels results in an
accepting the random and chaotic behavior of classical extremely low pressure drop, which is essential for
reactors, one can design and build reactors with regular end-of-pipe technology for exhaust systems. In contrast
spatial structures (Figure 1). to a packed bed no attrition occurs when vibration is
induced by for instance the moving automobile. The
Such structures may be designed in full detail, up to the straight channels prevent the accumulation of dust in
local surroundings of the catalyst species. This opportu- demanding applications such as those in coal-fired power
nity offers the potential of optimal performance of cata- stations for NOx control. A monolith can be mounted at
lytic functions and simplification of the fluid mechanics. any angle: vertical, horizontal, etc.
Such reactors are referred to as structured reactors
[1,2]. In nearly all respects, they outperform random/ Monoliths are mainly produced by extrusion, although
chaotic reactors. other methods are applied, for instance the manufacture
of metal monoliths from thin corrugated sheets. The size
Because of its dominance in automotive exhaust gas of the channels and the wall thickness can be varied
treatment, the monolith is the most popular structured independently. An optimum can be established between
reactor [3]. It consists of large numbers of parallel the amount of solid phase, void space, and wall thickness.
channels. In static mixers the units are combinations Because of the large scale of production these sophisti-
of corrugated sheets. A related structure (catalyst bales) cated structures are commercially available at modest
is used as a packing in catalytic distillation: the catalyst cost. It should be noted that monolith structures can
particles are placed in the pockets of a structured wire be used as such (the wall material is the catalyst or catalyst
packing [4]. Foams are three-dimensional cellular support) or the catalytic material is placed as a layer at the
materials made of interconnected pores. Catalyst bodies monolith walls (usually by washcoating). In the former
can also be made of knitted fibers, woven fabrics, etc. case the wall thickness is a degree of freedom, in latter the

Current Opinion in Chemical Engineering 2013, 2:346–353 www.sciencedirect.com


Monolith reactors Moulijn and Kapteijn 347

Figure 1

400 cpsi

1mm

Conventional

1.27 mm
2740 m2/m3

1mm

Monolith High-performance Permeable walls

1 mm

Foam cell
Pore

2.5 mm

Static mixer Foam Fibre structure

Catalyst bale Single capillary Microfabricated reactor


Current Opinion in Chemical Engineering

Structured packings/reactors.

thickness of the catalyst layer is an additional degree of In slurry reactors the particle size is in the micrometer
freedom. range but in trickle-bed reactors this is unfeasible,
because this would lead to a too large pressure drop.
A prominent trade-off in heterogeneous catalysis reactor Possible solutions are ring-shaped catalysts, ‘egg-shell’
design concerns the catalyst particle size. Table 1 gives catalysts, and catalyst particles with porosity of a fractal
typical time scales for diffusion in heterogeneous cata- design including diffusion channels, typically mesopores
lysis. or macropores [11,12]. These structures make sense, but
in general they lead to a sub-optimal design.
The characteristic contact times for industrial catalytic
reactions are typically in the range of minutes to seconds. An elegant alternative approach is to go away from ran-
These values suggest that particle diameters, in particular dom packed beds by turning to structured reactors. The
when the reactants and products are in the liquid phase, thickness of the wall of a monolith can be chosen inde-
have to be in a micrometer rather than in the millimeter pendently of the diameter of the channels. The wall
range. thickness determines the molecular transport rate, and

www.sciencedirect.com Current Opinion in Chemical Engineering 2013, 2:346–353


348 Reaction engineering and catalysis

Table 1

Characteristic time scales for diffusion distances in constrained spaces

Characteristic catalyst dimension, L


2
Phase of diffusing species Deff (m /s) 1 mm 100 mm 10 mm 1 mm
Gas 10 5 50 ms 500 ms 5 ms 50 ns
Liquid 10 9 500 s 5s 50 ms 0.5 ms
Liquid in typical catalyst pore 10 10 5000 s 50 s 0.5 s 5 ms
‘Liquid’ in zeolite pore <10 11 >50 ks >500 s >5 s >50 ms

the channel size the pressure drop. In packed beds, both flow conditions is high for two reasons [23]. First, the
dimensions are coupled. The possibility offered by mono- liquid layer between bubble and catalyst coating is thin,
liths to choose the length scales independently introduces generating fast mass transfer. Second, the liquid in the
a degree of freedom that allows maximum catalyst per- slugs circulates internally, leveling out any radial gradi-
formance with minimal pressure drop [13]. ents. The gas bubbles push the liquid slug forward as a
piston, resulting in essentially plug-flow characteristics.
From first principles, the desired thickness of a catalytic
coating can be estimated to be 10–100 mm. Thus, the wall Thus, Taylor flow combines good radial mixing with
of a commercial monolith (typically 100–200 mm) is too limited axial mixing [24], being completely opposite
thick to be used entirely as catalyst. Synthesizing a thin to single phase flow. For multiphase operation under
coating is a logical strategy, but at the cost of a low catalyst Taylor flow conditions, the mass transfer is an order of
loading per unit of reactor volume. An alternative magnitude faster than for single-phase liquid flow. The
approach could be to apply monoliths with walls that same conclusion holds for a comparison of monoliths with
are permeable and allow convective transport. Indeed, conventional reactors, kla for trickle bed, slurry and
such monoliths have been developed (Figure 2) [14–16]. monolith reactors typically are 0.01–01, 0.03–0.3 and
For fast reactions they showed excellent performance >1 s 1, respectively.
[17]. This conclusion is in agreement with a general
analysis of the optimal design of the distribution of the These high mass transfer rates were obtained at negli-
catalyst material in the reactor space [18,19], showing that gible pressure drop. In sharp contrast, other high-inten-
for maximal productivity a high open porosity at the level sity contactors, such as agitated tanks and bubble
of the catalyst is most important. columns, generally consume significant amounts of
energy to create high gas–liquid contact areas. This con-
One might wonder about the laminar flow profile in the trast is explained by the difference in flow regimes. In
small channels: would not it be unfavorable in comparison turbulent contactors bubbles are constantly broken up by
with the turbulent flow conditions prevailing in most the random turbulent flow fluctuations in the liquid,
industrial reactors? Table 1 shows that channels with keeping the coalescing bubbles small, but it is inefficient.
dimensions in range of millimeters do not pose any The largest part of turbulent kinetic energy is dissipated
problem for most gas-phase processes, because in the within the liquid itself. In contrast, in the small monolith
usual designs the channel diameter is 1–3 mm. However, channels, bubbles do not coalesce and no energy input is
there are exceptions. For instance, in SCR configurations needed to maintain a small bubble size [24].
for coal-fired plants dust concentrations are high and, as a
consequence, the channel diameters are relatively high Reactors and reactor configurations
(in the order of 6 mm), associated with external mass Monoliths are flexible to operate. They are well suited to
transfer limitations [20]. In operations with liquids, Table semi-batch, batch, continuous, and transient processing.
1 suggests that the laminar flow regime as a rule might be Catalytic conversion can be combined with in situ separ-
problematic. Remarkably, for the often encountered mul- ation, catalytic reactions can be combined, and heat
tiphase (gas/liquid) systems this is not the case, as follows integration is possible
from an evaluation of the hydrodynamics.
Scale-up
For multiphase systems in monoliths the two important Scale-up of monolithic reactors seems straightforward.
flow patterns are film flow and Taylor flow (Figure 2). Usually to a first-order approximation the channels are
Film flow occurs at relatively high gas flow rates. The regarded as identical. However, it has been shown that
smooth channels allow liquid to run down with minimal the channels of a monolith slightly, but significantly vary
hydrodynamic interaction with the gas phase. In a trickle- in dimension (typically with a variance of 5–10% [25]).
bed reactor such a regime can only be achieved at low gas Besides this internal maldistribution, external maldistri-
flow rates [21,22]. Taylor flow is the commonly encoun- bution is important, for instance as the result of the inlet
tered flow regime. The rate of mass transfer under Taylor design. In contrast to a packed bed, a monolithic reactor

Current Opinion in Chemical Engineering 2013, 2:346–353 www.sciencedirect.com


Monolith reactors Moulijn and Kapteijn 349

Figure 2

Cocurrent
Countercurrent
Solids flow

Film flow Taylor flow

Structured packed and moving beds

Connuous reactor Batch reactor

Purge
Liquid feed

Gas feed

Gas recirculaon
Monolith
Gas recirculaon

Monolith

Heat exchanger

Monolithic srrer Coolant

Heat
Gas/liquid exchanger Gas feed
separator
Product Pump Pump

Inial gas mixture Clean gas


Uptake secon
(A + B) (B)
Purge secon
Gas outlet Regeneraon
Regeneraon secon gas
(regeneraon products)

Rotang monolith
Current Opinion in Chemical Engineering

Flow regimes and reactor configurations.

has no flow in the radial direction. When the initial gas injection is achieved by entrainment by the flowing
distribution of liquid in the radial direction is non-homo- liquid. All the channels should be identical, and the liquid
geneous, this distribution will propagate down the reactor droplets should irrigate the channels uniformly. A stack of
unchanged. Even for gas phase applications a careful inlet monolith slices with decreasing cell densities toward the
design is needed in order to prevent preferential flow liquid inlet has been shown to be satisfactory. For coun-
through part of the reactor (usually the center part). tercurrent operation, flooding has to be prevented, which
Designs of inlets and outlets of monolith reactors have can be done by applying a similar stack of thin monolith
been investigated extensively. In the Taylor flow regime slices with decreasing cell density toward the outlet

www.sciencedirect.com Current Opinion in Chemical Engineering 2013, 2:346–353


350 Reaction engineering and catalysis

(where flooding most often originates), facilitating effi- successfully carried out in a rotating monolith/zeolite
cient drainage of the liquid [22]. Similar stacks can be system (Figure 2) [49].
used as spacers between monolith blocks [22,26,27].
Monoliths are parallel channel reactors. In R&D scaling
down can be done by decreasing the number of channels,
Catalyst synthesis
ultimately to one channel. However, there is more value
In new technologies often novel preparation methods are
in a single channel system: it is well suited for continuous
drivers to innovation [28]. Fascinating results were
chemicals production in fine chemistry [50]. This reactor
obtained by the synthesis of carbon nanofibers (CNF
design is extremely flexible with respect to the residence
layers) with an open, network-like structure, allowing
time.
an excellent accessibility [29–32]. Metal organic frame-
works are a new class of crystalline porous materials with
The straight channels of a monolith are ideal for moving-
a high potential in adsorption, storage, separation, and
bed applications, but they are also favorable for hosting
catalysis [33–35]. In slurry operation the crystals suffer
particles in a fixed bed, Figure 2. The monolith allows the
from attrition, and coating of these materials is an obvious
combination of an optimized catalyst particles inventory
avenue for improving their applicability [36]. Excellent
and an optimal liquid hold-up, while still having the
results were found for MIL-101(Cr) grown on the chan-
relatively low flow resistance [51]. Blocks of monoliths
nels of a monolith [37].
filled with particles may find applications in catalytic
distillation or three levels of porosity reactors [3,52].
Coated monoliths should have the advantage of a tunable,
well-defined catalyst layer thickness. However, as a con-
Conclusions
sequence of the (usual) square channel geometry in
Monolithic reactors offer high precision combined with a
commercially available monoliths in the corners the layer
high efficiency. Compared to most other structured reac-
thickness is significantly greater than in the flat parts of
tors they are cost-effective and they can be obtained in a
the walls. On top of this, the macroporous structure of
large variety of materials (ceramics, metals, polymers [53],
extruded monolith can accommodate active sites. By first
carbon [54]). Table 2 lists major commercial and poten-
dipcoating the bare monolith with small (nonporous)
tially attractive applications.
particles a nearly ideal support is obtained, a ‘High-
performance’ monolith (Figure 2). The optimized mono-
Monoliths are the state-of-the-art reactors in many prac-
lith showed significantly improved selectivity [38].
tical applications in environmental catalysis, because of
the low pressure drops at high flow rates, the dust toler-
Reactor configurations ance and the easiness of positioning. Commercial appli-
The monolithic reactor can be used as a stirred reactor cations include the use as post-reactor because of the
type by application of a high recirculation flow rate — easiness of retrofitting and superior performance. Sim-
achievable without a large energy input, because of the ilarly, they are applied to replace slurry reactors because
low pressure drop [3,39]. Thus, a monolithic reactor, of their combination of a high selectivity and convenience
although usually made from ceramics (poor heat conduct- of operation. They are a valuable tool for process intensi-
ing), is a feasible alternative for highly exothermic reac- fication.
tions often carried out in slurry reactors [39–42].
Monoliths are not by definition adiabatic reactors. Metal Monoliths allow the efficient use of small catalyst
monoliths can be made from corrugated sheets but even particles, such as zeolites. Time-consuming research in
by extrusion of metal powders [43]. Without recycle extrusion can be avoided by starting from commercially
streams depending on the conditions such a monolith available monolith supports. When higher loadings are
can operate close to isothermal for exothermic reactions. needed, extrusion of the catalytic material is possible, and
the catalyst loading may be as much as 80–90%.
A monolith reactor that might be particularly useful, at
least in small-scale operations, is based on a monolithic Monoliths can be used as structured internals for moving
stirrer [44,45,46,47] (Figure 2). The monolith impellers bed applications, as catalysts filled with a second catalyst,
have a strikingly large geometric catalyst surface area. and as catalyst bales in catalytic distillation.
The long entrance region for mass transfer results in
excellent transport, even in single liquid phase. The fundamental aspects of reactor design are rather well
understood. The flow in monoliths is laminar, associated
Rotating contactors are applied for cyclic processes like with high efficiency and minimum chaotic characteristics.
adsorption/desorption in exhaust gas treatment [48]. This In a wide range of conditions in multiphase systems,
design combines a simple process lay-out and a product Taylor flow (segmented flow) prevails, allowing high rates
flow with constant composition. Monoliths are suited for of mass transport notwithstanding low energy consump-
this technology. Separation of n-butane and i-butane was tion. The Taylor flow regime is per definition cocurrent,

Current Opinion in Chemical Engineering 2013, 2:346–353 www.sciencedirect.com


Monolith reactors Moulijn and Kapteijn 351

Table 2

Realized and promising applications

Reactions Phases Sector (supplier) Category Scale Effect Ref.



Oxidation CO, HC; Gas Otto engines End-of-pipe >10 000 000 Robust efficient [9 ,56,57]
reduction NOx
Reduction of NOx with Gas Power plants End-of-pipe Widely applied Robust low Dp [20]
NH3 or urea
O3 decomposition Gas Air planes Intake air Standard in Low Dp [58]
air planes
Selective oxidation Gas Bulk chemicals Postreactor, packed >2 plants High yields [59]
of xylene bed replacement
Total oxidation VOC Gas Consumers Toilet, kitchen, chimney Commercial [60]
Adsorption Gas Personal protection Gas mask Successfully Low Dp [61,62,63]
demonstrated
Selective oxidation Gas Fertilizer industry Replacement Pt-gauze >10 plants Less Pt loss [64]
of ammonia
Acylation butanol Liquid Chemicals Biocatalysis Successfully Lipase support [47]
production demonstrated
Hydrogenation step Gas/liquid Bulk chemicals Replacement slurry reactor 200 ktpy Catalyst separation [65]
in AO process
Total oxidation VOC Gas/liquid Water purification Replacement conventional Successfully [66]
reactor demonstrated
Hydrogenation Gas/liquid Materials Polymers with C C or CN Successfully Tuning materials [67,68]
polymers demonstrated properties
Hydrogenation Gas/liquid Bulk chemicals Replacement slurry reactor Retrofitting in Catalyst separation [69]
of nitroaromatics fine chemistry
Selective oxidation Gas/liquid Photocatalysis Novel reactor with guided light Activity issue [70]
of cyclohexane

but the film flow regime can be realized either in co- or Overview of the status of monolith catalysis from fundamentals to appli-
cations should be read in combination with this opinion paper.
countercurrent mode, making the monolith a good struc-
3. Kapteijn F, Heiszwolf JJ, Nijhuis TA, Moulijn JA: Monoliths in
ture for novel technologies such as catalytic distillation,  multiphase catalytic processes — aspects and prospects.
extraction, absorption, aeration in gas–liquid (bio-) con- CATTECH 1999, 3:24-41.
tactors, and liquid–liquid interphase or phase-transfer The first popular manuscript on monoliths. Launched creative ideas for
monolith applications that have not been realized to date.
catalysis.
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catalyst-containing pockets of modular catalytic structured
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applications in fine chemistry and in the laboratory, two structured: woven active carbon fibre matt catalyst. Catal
new reactor types are presented, a convenient monolithic Today 2005, 105:325-330.
stirrer reactor and a single capillary reactor with a catalyst 6. Pangarkar KV, Schildhauer TJ, Ommen JRv, Nijenhuis J,
wall coating. Monoliths have inspired a tremendous  Kapteijn F, Moulijn JA: Structured packings for multiphase
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