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Vangerven2007 PDF
Vangerven2007 PDF
Received 30 March 2007; received in revised form 16 May 2007; accepted 26 May 2007
Available online 6 June 2007
Abstract
Photocatalysis is an attractive technology with potential applications in various disciplines, such as chemical synthesis, environmental technology
and medicine, and receives an impressive amount of exposure in the open literature. However, industrial implementation remains limited due to
scale up problems and the design of photoreactors. In this paper an overview is presented of recent advances in the design and application of novel
reactors and devices.
Two issues are essential: photon transfer limitations and mass transfer limitations (in the case of liquid phase reactions). In the field of mass
transfer optimisation, spinning disc reactors, monolithic reactors and microreactors have been investigated for their use in photocatalysis. Significant
advances are reported compared to conventional reactors. Studies focusing on performance improvement by optimising photon transfer, however,
remain limited. While optical fibers and LEDs have been explored, major breakthroughs are still lacking. More focus on the introduction of a
multitude of micro- or even nanoscale light emitting sources close to the catalyst particles is likely to be the way forward.
© 2007 Elsevier B.V. All rights reserved.
Keywords: Photocatalysis; Photoreactor; Process intensification; Microreactor; Spinning disc reactor; Monolithic reactor; Optical fibers; Nanoscale illumination
K.U.Leuven, de Croylaan 46, 3001 Leuven, Belgium. • process selectivity to the required products can drastically
Tel.: +32 16 32 23 42; fax: +32 16 32 29 91. increase (e.g., due to a different chemistry, or low/ambient
E-mail address: tom.vangerven@cit.kuleuven.be (T. Van Gerven). process temperature);
0255-2701/$ – see front matter © 2007 Elsevier B.V. All rights reserved.
doi:10.1016/j.cep.2007.05.012
782 T. Van Gerven et al. / Chemical Engineering and Processing 46 (2007) 781–789
limiting scale-up of photoreactors and reviews recent efforts to by the authors of the present article based on the data given in the reference.
d The ratio of values is due to the variety of tested catalyst concentration in
tackle these issues.
the slurry.
e This value is explicitly equalled to the illuminated surface per volume (κ) in
2. Identification of the current engineering limitations the reference.
of photocatalytic processes f The illuminated surface per volume (κ) will be lower than this value due to
with Hc is the average irradiance of light on the catalyst surface with ηill is the illumination efficiency (m−1 ), κ the illuminated
(W m−2 ), Plamp the emitted radiant power of the lamp (W) and surface per unit of reaction liquid volume inside the reactor
l is the distance from lamp to the catalyst surface (m). (m2ill m−3 −1
reactor or m ), Pcat the radiant power incident on the
A small distance between light source and catalyst sites is catalyst surface (W), Plamp the radiant power emitted from the
thus preferred. lamp (W), Amin E the catalyst surface that receives at least the
Second, light can be absorbed on the way to its final destina- band-gap energy (m2 ) and Acat is the total catalyst surface (m2 ).
tion. This process is governed by the law of Lambert-Beer (Eq.
(3)): 2.2. Limited contact between activated catalyst and
reagents (mass transfer limitations)
P0
log10 = εlc (3)
P This issue mainly relates to the application for process fluids
as mass transfer limitations will be of minor importance in gas
with P0 is the radiant power before absorption (W), P the radi- streams. The presence of a gas phase in a liquid environment
ant power after absorption (W), ε the molar absorptivity of the can affect the optimal reactor design but this will not be further
absorbing species (l mol−1 m−1 ), l the path length through the investigated in this paper, as no publications report on this issue
material containing the absorbing species (m) and c is the con- in detail.
centration of the absorbing species (mol l−1 ). Once the catalyst is activated by the incident light, maxi-
In many photoreactor designs the light has to travel through mized contact between catalyst and reagents in the process fluid
the fluid or gas containing reagents and other species, and also should be achieved. Furthermore, removal of the formed reaction
through a transparent wall. Part of the originally emitted light can products should be maximised as well. The issue of improved
be absorbed by these components before it reaches the catalyst. mass transfer obviously transcends photocatalysis. It is widely
In addition, it is very difficult to achieve uniform irradiance researched in chemical engineering and various devices have
of the entire catalyst surface. Uniformity is important because a been developed or proposed to reach that goal. Some of them
minimum energy level is needed to activate the catalyst. Diony- have been applied to photoreactors, such as the spinning disc
siou et al. [10] have measured the light irradiance distribution reactor, the monolith reactor and the microreactor. The issue
of two low pressure mercury UV tubes positioned horizon- therefore appears less critical than the photon-related issues, as
tally at a distance of 10 cm from a TiO2 coated surface of a more solutions have been proposed. However, an ideally inten-
disc in a spinning disc reactor. They observe a highly non- sified reactor should be able to integrate both maximized light
uniform illumination with light irradiance varying from 30 to efficiency and mass transfer within one piece of equipment.
1500 W/cm2 and an average value of 895 W/cm2 . Raupp et Mass transfer optimisation in catalysed reactions is mostly
al. [11] have modelled the UV light irradiance field from three quantified by the amount of catalyst surface area per unit or
UV lamps positioned horizontally at 5 cm from a monolith sur- reactor volume. Table 1 gives an overview of this value for
face of 32 cm × 48 cm. It appears that the variation on the surface various reactor configurations. A wide range of this value is
is substantial. Greater uniformity can be achieved by increasing observed within each of the reactor types. The lower values in
the distance between the lamps and the monolith surface (but these ranges indicate that the aim of the specific research was not
decreasing average irradiance) or by adding more lamps (but to maximize mass transfer but rather to explore a specific part
increasing energy costs). of the reactor, such as photon transport. This value is already
We propose the illumination efficiency, ηill , as a new param- incorporated in the κ value related to the illuminated surface per
eter (Eq. (4)), taking into account the illuminated surface per volume, described in the previous paragraph. Furthermore, in
volume (κ, m−1 ), the average power efficiency (defined as a ratio immobilized catalytic reactors, the ratio between the amount of
of average incident radiant power on the catalyst, measured with reactants in the reacting liquid and the amount of reactants that
a radiometric probe at different sites, to emitted radiant power), actually come in contact with the catalyst coating is controlled
and the incident uniformity. The latter issue needs further inves- by the degree of turbulence. Lin and Valsaraj [12] define in that
tigation to measure and quantify. One might think of defining respect external mass transfer (diffusion of reactants from the
uniformity as a factor of the catalyst surface that receives at least bulk liquid through a boundary layer to reach the liquid–catalyst
the minimum energy (i.e., the band-gap energy), to the total cat- interface) and internal mass transfer (inter-particle diffusion of
alyst surface area. Clearly, to date quantifiable results for this reactants within the catalyst film to the active surface sites where
parameter cannot be calculated from the data given in literature they can adsorb and eventually react). Intra-particle diffusion
for the specific designs proposed, due to the fact that not all data was neglected by these authors since their TiO2 was considered
has been measured for each reactor configuration. However, it non-porous. Increasing the flow velocity, and thus the Reynolds
is anticipated that its use would make a comprehensive compar- number, could reduce the external mass transfer resistance [12].
ison possible between the different configurations proposed in As the latter parameters (flow velocity, Reynolds number) are
784 T. Van Gerven et al. / Chemical Engineering and Processing 46 (2007) 781–789
per unit reactor volume and scale-up potential [12]. The optical
fiber monolith reactor that Lin and Valsaraj [12] developed gives
a 10-fold increase on the illuminated catalyst surface per unit
of reactor volume compared to an annular reactor, and a 100
times increase of the apparent quantum efficiency. An improved
variation of the design of Lin and Valsaraj [12] could be that
the catalyst is only coated on the monolith wall and not on the Fig. 2. Nanoscale illumination reactor (after [32]).
fibers, in order to maximize light emission from the fibers and
avoiding back-irradiation. This is currently under evaluation in
the Delft laboratories. catalyst surface enhances the options for other reactor types (e.g.,
Finally it has been reported that the light intensity is inversely monolithic reactor, spinning disc reactor), which are otherwise
related to the quantum efficiency of photocatalytic reactions difficult to combine with microscale illumination. It remains
[20,28], due to the high recombination rate of charge carri- to be verified whether nanoscale UV sources can provide suf-
ers at high intensity. A lower intensity is thus preferred to ficient energy (i.e., the required wavelength and intensity) for
decrease recombination, but this obviously will decrease cat- the desired reaction to occur. Gole et al. [34] suggest the intro-
alyst activation as well, with consequently a lower rate of duction of nitrogen doped titania nanostructures into the pores
charge pair generation and thus will lower overall photocat- of porous silicon (PS) in order to develop a device to produce
alytic reaction rate. It appears that optical fibers can overcome visible light by electroluminescence of PS thus activating the
this problem by decreasing the light intensity but increas- photocatalyst particles. This device could then be incorporated
ing the number of fibers [20]. However, this will then again in a microreactor. A scheme of this promising photoreactor prin-
have a negative effect on the reactor volume available for the ciple is shown in Fig. 2. Porous silicon emits visible light, hence
reagents. the necessity of using nitrogen doped TiO2 samples to shift the
Research on the specific area of micro- or nanoscale illu- absorption spectrum from UV to the visible spectrum. Stability
mination in photocatalysis is rather scarce. The concept can of this modified titania is, however, an issue to be evaluated more
be considered as new with only a handful papers present in in detail.
the literature. Microscale illumination has been investigated in
the papers of Gorges et al. [29], Chen et al. [30] and Mat- 4. Overcoming mass transfer limitations
sushita et al. [31] with encouraging results for the oxidation
of 4-chlorophenol and PCE, and the reduction of benzaldehyde In order to overcome the mass transfer limitations in fluid sys-
and nitrotoluene. They use commercially available UV emitting tems, several intensified reactor types have been proposed. The
LED devices. In Gorges et al. [29] the light source consists of most reported and investigated types of reactor for photocataly-
11 LEDs producing a current of 30 mA each and a potential of sis are slurry systems, spinning disc reactors, monolithic reactors
3.7 V, whereas Chen et al. [30] use 16 LEDs producing a current and microreactors. Slurry systems are by far the most used in
of 20 mA each and a potential of 3.7 V. Matsushita et al. [31] do photocatalysis research, mainly with respect to the potential of
not specify details of the used array. Chen et al. [30] report that photocatalysis for specific oxidation or reduction reactions. An
the LEDs have an optical output power of 12 mW each, which is obvious advantage of these systems is the good contact between
16% of the electric input power (i.e., current intensity times elec- reactants and catalyst, illustrated by the high surface area per vol-
tric potential, 74 mW each). This is comparable to the ratio range ume that can be achieved (Table 1). However, scaling up such a
of 7% (black light) to 23% (germicidal lamp) for traditional gas device implies a separation step of the catalyst from the reaction
charge UV light sources. However, when taking into account the products, with major technical and economical problems as a
absorbed photon energy on TiO2 to electric input ratio the figure result. Also, it is difficult to uniformly irradiate suspended par-
of 23% decreases to 15%, because one-third of the optical output ticles, although some configurations may (partly) overcome this
in the germicidal lamp is lost as heat (due to the unnecessary high disadvantage (Fig. 3). In the fluidised bed reactor, for example,
energy level (λ = 254 nm), much higher that that used for cata- the catalyst is placed on supporting beads. These beads form the
lyst activation (λ = 387 nm, equivalent to the 3.2 eV band-gap)). bed material and are fluidised by way of an air stream. An aque-
Other advantages are that these devices are small (miniaturisa- ous or gaseous pollutant flow can be introduced in the fluidised
tion of equipment), robust, and long lasting (hundred thousands reactor, either in batch or in continuous set-up [36–38]. Although
of hours compared to thousands of hours in the case of classi- the fluidised bed reactor is a dispersed-phase reactor with all its
cal lamps). The use of microscale illumination in microreactors associated problems with respect to illumination [9], the gener-
provides both a large catalyst surface area per unit or reactor ation of bubbles in the fluidised bed reactor will enhance light
volume and a high illumination efficiency, also related to the penetration compared to the conventional slurry reactor [38]. A
small angle of emittance of the UV-LEDs. However, catalyst similar aim is achieved in a cocurrent downflow contactor pho-
surface and light source remain physically separated, thus still tocatalytic reactor [39]. The fountain photocatalytic reactor is
leaving potential for improvement (even more increase of the another configuration building on the conventional slurry reac-
illumination efficiency). tor design that combines minimal mass transfer limitations with
Nanoscale illumination does explore this as yet unharvested a very large illumination surface area per unit volume catalyst
potential [32–35]. In addition, the integration of light source and [40].
786 T. Van Gerven et al. / Chemical Engineering and Processing 46 (2007) 781–789
Fig. 3. Examples of improved slurry reactors: (a) fluidised bed reactor and (b) fountain reactor (after [38,40]).
Other researchers, focusing on scaling-up of photocatalysis, that a high catalyst surface area per reaction liquid volume can
advocate the use of immobilised catalysts. Dijkstra et al. [41] potentially be attained. It is also easy to scale up [10], either by
have shown that immobilized systems can attain comparable increasing the disc diameter (although this is technically not an
quantum yields as slurry systems. A spinning disc reactor has infinite option) or by installing multiple discs (although costs
attractive features such as limited mass transfer limitations due would increase simultaneously). The spinning disc reactor can
to the combination of thin film and turbulent flow with subse- be operated in two ways (Fig. 4): horizontally [42,43] with the
quent high mass transfer coefficient [42], increase of conversion, liquid introduced in the center of the disc, which then spreads
better and more reliable product quality [43], introduction of the over the top surface of the disc until it falls off at the edges of
reaction liquid in a gentle non-oscillating motion thus diminish- the disc, or vertically [10,44] with half of the disc immersed
ing the occurrence of the phenomenon of catalyst attrition [10], in the liquid and the top half entraining the reactor liquid and
which has been reported in, e.g., annular reactors. Table 1 shows exposed to the UV-source. The difference in efficiency between
both configurations is not clear. It can be anticipated that it is the thickness of the TiO2 coating. Sauer and Ollis [48] refer to
more difficult to devise a continuous system with vertical discs a reported light absorption of 99% within a 4.5 m thick TiO2
and that less surface is illuminated (i.e., only half discs), although coating. Third, although limited absorption was present in the
multiple vertical discs can be combined in stacks, thus increas- investigated case of PCE pollution in air, this geometry is dis-
ing capacity with limited increase of reactor volume. A deviation advantageous when UV-radiation is absorbed by the pollutant
to this stack-configuration of rotating discs is the rotating drum, or by the medium in which they are present (e.g., liquid). Sauer
as reported by Zhang et al. [45]. The drum can carry multiple and Ollis [48] suggest using two light sources, one on either
teeth (a screw-like configuration) to increase the surface area to end of the monolith reactor. This would roughly double the illu-
be coated with catalyst. Problems with a uniform illumination mination efficiency. The optical fiber monolith reactor that Lin
of the discs were reported by Dionysiou et al. [10] as described and Valsaraj [12] developed gives a 10-fold increase on the illu-
earlier. minated catalyst surface per unit of reactor volume compared
The monolithic photoreactor (Fig. 5) provides a high surface- to an annular reactor, and a 100 times increase of the apparent
to-volume ratio (10–100 times more than plates or beads quantum efficiency.
substrates with the same outer dimensions) [12] although from Only very recently microreactors (Fig. 6) have been investi-
Table 1 it appears less attractive than spinning disc reactors or gated in performing photochemical and photocatalytic reactions.
microreactors. It allows high flow rates with low-pressure drop, The main advantage of microreactors is the high surface-to-
and is easy to scale-up. It can also be combined with other reac- volume ratio. In the case of photochemical reactions this leads to
tor configurations such as a cocurrent downflow bubble column an efficient illumination [49–52]. In the case of photocatalytic
reactor [39]. Disadvantage of the monolithic photoreactor is the reactions, this implies efficient catalytic exposure to radiation
low light efficiency. Hossain et al. [46] predict the light flux [29], but in addition it also leads to maximized reagent/catalyst
in the monolith channels by modelling. At the entrance of the contact [53,54]. The small size of the channel also provides
channels, the light flux already decreases by 50% because of greater control over variables such as temperature control and
shadowing of the incoming diffuse light at the channel entrance flow rates [53], due to the fast heat and mass transfer, and
by the wall. At a distance of 1–2 aspect ratios (length per chan- the presence of laminar flow [49,50]. The light source itself
nel width) in the square channels, only 10% of the initial light can also be UV-LED, thus miniaturizing the whole photocat-
flux remains, and at a distance of 3–4 aspect ratios the light flux alytic set-up [29,31]. The patented configuration of Barthe et al.
has decreased to 1% of the initial flux. In order to overcome this [53] can contain 23 g/l TiO2 , which is 11 times more catalyst
shortcoming of monolith reactors several improved designs have per unit of volume than in a conventional batch reactor [55].
been suggested. Imoberdorf et al. [47] conceived a multiannular Gorges et al. [29] and Matsushita et al. [31] report a (illumi-
reactor with four tubes from UV-transparent walls concentrically nated) catalyst area-to-reactor volume of almost 12,000 m2 /m3
arranged, which resembles a very basic transparent monolith. and 14,000 m2 /m3 , respectively, while this value in Takei et al.
The UV source is placed at the centreline and irradiates the three [54] even reaches 0.25 m2 /ml (i.e., 250,000 m2 /m3 ). These num-
annular channels where the polluted air flows. TiO2 is coated on bers are among the highest in Table 1. Takei et al. [54] found a
the inner and outer surfaces of the annular walls. This geometry 70-fold increase in conversion rate compared to a slurry reac-
has three disadvantages. First, the TiO2 coating on the inner wall tor with the same selectivity and yield. Li et al. [56] report
of the duct is illuminated on its backside, whereas the reagent a 60 (530 m diameter capillary)- to 160 (200 m diameter
pollutants adsorb on the coating from the other side. Second, due capillary)-fold increase in conversion rate compared to a slurry
to the TiO2 coating, the UV flux is bound to be diminished, and reactor. Obvious drawback is the relatively small throughput
this more in the outer annular ducts. Calculations by the authors of microreactors [57]. The flow-rate in Takei et al. [54] is
of the present publication on the basis of the reported results 1 l/min (i.e., 526 ml/year), although this was evidently per-
indicate that only 10% of the initial photon flux reaches the formed in a lab set-up without focus on scale up. Microreactors
inner TiO2 coating of the second duct, and less than 1% reaches currently implemented in industry can produce up to 5000 or
the inner catalyst coating of the third duct. Of course the amount even 20,000 tonnes/year. It is clear that microreactors have large
of light flux going through the catalyst coated wall depends on potential.
788 T. Van Gerven et al. / Chemical Engineering and Processing 46 (2007) 781–789
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