Vol.

05 INTERNATIONAL JOURNAL OF PHOTOENERGY 2003

Photocatalytic reactors

M. Bouchy† and O. Zahraa‡

Département de Chimie Physique des Réactions - UMR 7630 CNRS-INPL
ENSIC, 1 rue Grandville, BP 451, F-54001 - Nancy Cedex, France

Abstract. Fundamental concepts for the design of photocatalytic reactors are recalled: specific rate, mod-
eling of the distribution of the irradiation, description and modeling of transport phenomena on the macro-
scopic and macroscopic scales. These are required for establishing the reactor mass balance. A brief survey
of various reactors is given for solar or artificial light, gas- or liquid-phase, slurry or fixed-bed.

1. INTRODUCTION 2.2. Rate of photocatalytic degradation. The

rate of photocatalytic degradation depends on several
Photocatalysis has been a subject of increasing interest parameters for a given pollutant and catalyst which are
during the last twenty years. It has indeed various po- mainly:
tential applications such as metal recovery, abatement
of NOx , synthesis of ammonia but the recent develop- • pollutant, oxygen (and other compounds) con-
ments have been induced mainly by the application to centrations,
the abatement of organic pollutants both in the aque- • temperature,
ous and the gaseous phase. This development partic-
ipates to the general concern about the environment • irradiation wavelength and flux.
and the increasing constraints on the toxicity of wastes. 2.3. Specific rate. These parameters are not usu-
The academic studies have been much developed in the ally uniform within the reactor. At any given point, the
fields of organic chemistry, physical chemistry, chem- rate per unit catalyst amount q, or specific rate rspe ,
ical kinetics and catalyst preparation, but few studies takes a local value so that the total rate in the reactor
have been dedicated to chemical engineering and the is the integration of the elementary rates dr = rspe · dq
development of reactors. Concomitantly, few industrial over elementary amounts dq of catalyst.
processes have been developed. The effect of the irradiation on this elementary cata-
The aim of this presentation is to give some aspects lyst amount is determined by the specific rate of energy
of studies related to chemical engineering of photo- absorption iabs = dIabs /dq, where Iabs is the absorbed
catalysis; far from being exhaustive, it aims at giving energy (E · s−1 or W), also called LVREA (Local Volumet-
an insight into the extent and importance of this topic. ric Rate of Energy Absorption).
The presentation will deal with three selected sub- Note that this “amount” of catalyst can be chosen
jects: light distribution within a reactor, mass trans- as catalyst mass, suspension volume or support area
fer processes and a brief survey of photochemical (immobilised catalyst), depending on the type of reactor
reactors. used.

2.4. General system. Another problem is that

2. BASIC CONSIDERATIONS mass transfer phenomena can intervene in the process
by reducing the effective local concentration so that the
2.1. Photocatalytic process. The photocatalytic analysis of the reactor must take into consideration:
process results from the excitation by UV-visible light
• the local specific rate,
of a solid semiconductor, generating free electrons and
holes, which leads to redox processes on the surface • the irradiation distribution (the space-dependent
and the attack of adsorbed molecules. Direct attack LVREA),
of organic molecules on the surface, or formation
of highly reactive hydroxyl radicals results, in the • the laws of mass-transfer phenomena (external,
presence of oxygen, in the oxidation of the organic internal transfers),
molecules, which, in most cases, leads to a complete
• the mass-balance over the whole of the reactor.
mineralization.
A complete analysis allows accurate information on the
† laboratory scale to be obtained and the scaling-up of an
E-mail: Michel.Bouchy@ensic.inpl-nancy.fr
‡ effective reactor to be carried out. However, the whole
E-mail: Orfan.Zahraa@ensic.inpl-nancy.fr
192 M. Bouchy and O. Zahraa Vol. 05

problem is complex and requires knowledge of the con- solid angle I(ω) (E · m−2 ·sr−1 ·s−1 ) along the direction
stitutive laws and of the operative parameters so that defined by the unit vector ω, which includes:
simplifying assumptions are often made so as to get a
feasible study and practical reactors are designed with- – loss by absorption (coefficient κ),
out a complete ab-initio analysis.
– loss by scattering-out (coefficient σ ),

3. SPECIFIC RATE – contribution by scattering-in from fluxes in all

the directions ω
in space (probability dependent
The basic information which allows a photocatalytic re- on σ and on the angle between ω
and ω, with
actor to be designed is an analytical expression for the the probability per unit solid angle (or phase-
specific rate of reaction. Data can be found in the liter- function) p(ω
, ω) [1, 3]:
ature but are often given as the total rate within the re-
actor, resulting from an average value of the irradiation dI(ω)
= −(κ + σ ) · I(ω)
rate instead of taking the irradiation distribution into ds

 
1
account [1]. A general picture is as follows, although +σ · · p(ω
, ω) · I(ω
)dΩ
,
some more elaborate rate expressions are also found: 4π 4π

where dΩ
is an element of solid angle in the di-

• a concentration dependence of the Langmuir-
rection ω
.
Hinshelwood type [2] which leads to first-order
kinetics at low concentration and zero-order To solve this equation requires experimentally deter-
kinetics at high concentration, with a similar mining or modelling the absorption and scattering co-
additionnal effect of oxygen concentration, of- efficients and also the phase function p. On principle,
ten referred to as the LHHW model (Langmuir- a theoretical expression for p can be derived from
Hinshelwood-Hougen-Watson), MIE theory but due to the complexity of the deriva-
tion, approximate functions have been used (for large
• a low activation energy,
spheres [4]) and also simple isotropic scattering.
• an order with respect to absorbed irradiation In addition, solving of this integro-differential equa-
varying from 1 at low flux to 0.5 at high flux, tion requires knowledge of a boundary condition. This
which is attributed to recombination of reactive is the incident flux Iw (ω) on the reactor walls. The
species (especially hole-electron recombination). LVREA is then:

iabs = κ · Iω dΩ.
4. IRRADIATION DISTRIBUTION 4π

There is no feed-back effect between irradiation and Note also that the parameters are dependent on the
chemical conversion as long as the reactants (or prod- wavelength λ and that, for a polychromatic source
ucts) do not absorb the irradiation in the wavelength (sun, fluorescent lamp) the spectral density Iλ (ω) =
range where the catalyst is excited. The catalyst con- dI(ω)/dλ and corresponding iabs,λ should be used in-
centration is therefore the only parameter and as this stead of I(ω) and iabs , which would then be integrated
catalyst is by essence a stable compound, the light over the wavelength range.
distribution does not depend on the extent of re- The lamp irradiation flux on the reactor wall Iw (ω)
action. This is indeed generally the case in low- can be known from the geometry of the reactor and
concentrated fluids and in near-UV range (wavelength the distribution of the emission from the light source.
of 350–400 nm). If this were not the case, the concentra- The solar emission is well defined as a one-direction
tions and light distributions would be linked together uniform flux, but the emission of an artificial lamp is
through the absorption law for the fluid phase, which more difficult to assess. The lamps being considered
would add to the complexity of the system. are of a cylindrical shape and have been simulated
as an isotropically emissive medium, either a cylindri-
4.1. Suspension. In the case of a suspension (or a cal volume (which could ultimately be considered as a
nearly-continuous fixed bed), the LVREA depends on thread [5]) or a cylindrical surface (fluorescent lamp).
the emission of the light source, both in intensity and The emission is on principle isotropic in the whole
spatial distribution, and on the absorption and scatter- space but a simplified model assumes emission to oc-
ing properties of the reactor filling. If there is no ab- cur perpendicularly to the lamp axis only.
sorption by the compounds in the fluid, the LVREA is Once the system is defined, it is a difficult mathe-
dependent on the catalyst only. However, this calcula- matical problem to solve it. If no simplifying assump-
tion is much complicated by the scattering. tions are made, a numerical method is necessary. The
The master equation is an energy balance along a Discrete Ordinate Method is a convergent algorithm
path ds on any energy flux per unit surface, time and based on exchange between finite volume elements [1]
Vol. 05 Photocatalytic reactors 193

or discrete directions in space [3] (about 220). Alter- Note that increasing the surface area of the catalyst
natively, a Monte Carlo approach can be used [3, 5]: is profitable as this increases the pollutant adsorption
in this method, the fate of individual photons is sim- and therefore its degradation and usual catalysts are
ulated then all these events are averaged over a large therefore of a porous or dispersed nature although this
number of photons to get the LVREA, a rigorous but increases the possibility of mass-transfer limitation.
time-consuming method. Mass-transfer phenomena can be classified as exter-
Analysis of the light distribution is of importance: nal, within the fluid in the vicinity of the catalyst pel-
although a pseudo Beer-Lambert can be used to sim- lets or deposits (then enhanced by fluid stirring), and as
ulate absorption under some conditions (see below), it internal within the catalyst pores (independent of the
can be observed that the increase in catalyst loading can stirring).
result in a maximum in the rate of the reaction instead
of a limiting value [6, 7]. 5.2. External mass transfer. The rate of external
mass transfer is generally expressed according to the
4.2. Thin film- deposited film. A simplification of model of the boundary layer on the catalyst surface.
the general treatment has been suggested [8] where the The rate is then expressed as:
contribution of scattering-in to the energy intensity can
be neglected by a careful design of the reactor (with r = kext (Cb − Cs ) (mol · m−2 ·s−1 ),
small light path), which is appropriate for laboratory
where Cb and Cs represent the bulk and surface con-
kinetic studies leading to a pseudo Beer-Lambert law.
centrations, respectively.
Such an approximation, has also been used for thin de-
The rate constant kext depends on the flow regime
posits [5, 9], which gives a satisfactory representation
of the fluid, generally characterised by the non-
of the global properties of the film as measured by an
dimensional Reynolds number Re. It is given by various
integrating sphere [10]. A simple model [11] considers
empirical expressions such as [9]:
a finite number of elementary slabs having the same
properties of absorption and reflection and exchang-
kext = 3.49 × 10−7 Re0.77 (m · s−1 ).
ing light flows. In an alternative model, originally de-
signed for suspension films [12], the light is assumed As the rate constant kext increases with the flow turbu-
to propagate normally to the film plan only: scattering- lence, a good stirring is usually enough for the effect of
in is neglected and the total light flow is assimilated to external transfer to vanish, i.e. (Cb −Cs )/Cb  1. Exper-
opposite flows coupled to each other by scattering-out. imentally, this can be verified by checking that the rate
This latter model has the advantage of leading to an is not dependent on the flow rate or stirring beyond
analytical expression for the LVREA and has also been some minimum value.
applied with some refinement to film deposits [13]. In some instances, the oxygen supply has been sug-
This model has proved satisfactory although out- and gested as a source of rate limitation. Note that the flow
in-scattering by thin deposits has been found to be in oxygen to the solid particle or deposit results not
nearly isotropic [14]. Note that the determination of only from external transfer but also, for aqueous solu-
the global properties of a deposited film can also be tion treatment with bubbling gas, from dissolution at
used to carry out the simulation of reactors equipped the gas-liquid interface. This can to be taken into ac-
with sets of transparent supports of moderately count [5] in mass balance with a specific rate of disso-
absorbing films. lution given by the basic expression:
 
r = kG/L CG/s − Cb (mol · m−2 ·s−1 ),
5. MASS-TRANSFER PHENOMENA
where kG/L is the rate constant and CG/s the oxygen con-
5.1. Coupling with mass transfer. Any consump- centration in the liquid phase in equilibrium with the
tion of reactant results in a decrease in the local gas phase by the gas-liquid interface.
reactant concentration. A concentration gradient then
appears and results in a flux of matter. It can be as- 5.3. Internal mass transfer. Internal mass-transfer
sumed that the QSSA (quasi-stationary-state approxi- is more likely to result in rate limitation in a deposited
mation) is obeyed so that the “photographic” picture of catalyst than it does on a suspended catalyst [15]. Con-
the local situation at any time reveals an exact mass- trary to external mass-transfer, it is not possible to ob-
balance i.e. an equality between transported reactant tain direct evidence of a limitation as the parameters
through mass-transfer phenomena and consumed re- involved (dimension of pores, molecular diffusion coef-
actant through the photocatalytic process. The conse- ficient) cannot be varied independently of other kinetic
quence is that the local concentration in the immediate parameters. An indirect way of investigation is to vary
vicinity of the catalyst surface is lower than it is in the the thickness of the catalyst film (an increasing effect
bulk of the fluid. of internal mass transfer would lead to a limiting value
194 M. Bouchy and O. Zahraa Vol. 05

of the quantum yield of degradation), or to compare Concentrations are assumed to be uniform in the
the effect of irradiation from the fluid side and from first two types. On the contrary, they vary during the
the (transparent) support side in which case an effect progress of the fluid within the PFR reactor so that the
of internal mass transfer would lead to a lower quan- mass balance must take into account the flow of the
tum yield of degradation. A measurable [9] or negligi- reactive medium. Non-ideal reactors will include addi-
ble effect [11] has been observed by this technique. The tional features such as lateral mass transport, or seen
comparison of the rate of adsorption rads and of pho- as a compound system (reactor with mixing tank). In
tocatalytic degradation rdeg can also be compared as real reactors the mass transport is bound to the fluid ve-
rads is mainly diffusion controlled (in physical adsorp- locity distribution. Perfectly laminar or turbulent flows
tion). A partial limitation in suspension of aggregates are often considered, as real flow computation through
has thus been shown [6]. Navier-Stokes equation is a very complex problem on
The consequence of a mass transfer rate limitation its own.
is to alter the true value of the orders with respect to A complete ab-initio modelling of the reactor has
the reactant and the irradiation rate (with a limiting seldom been carried out but a chosen example will be
value of 1 for reactants and 0 for the irradiation rate). given as an illustration in the case of a fixed-bed reactor
As a consequence, the effect of internal transfer, if not where the catalyst is deposited on packed rings in an
specifically studied, is often included in an “apparent” annular reactor of cylindrical symmetry [5]. Note that if
specific rate of reaction. the rings are small enough, the bed is quasi-continuous
The phenomenon has been modelled either by as- so that the treatment is identical to that of a suspen-
suming an exponential expression for the decrease in sion.
concentration with the increase in depth within the cat- The master equation (1) of mass balance for each
alyst [9]. reactant is written as follows (bulk concentration C, ra-
In thermal catalysis, the non-dimensional Thiele dial variable r and longitudinal variable z):
and Weisz moduli ϕ and ϕ
are defined:  

dCb 1 dCb d2 Cb
vL −D + hup
rs L2 L2 dz r dr dr2
ϕ2 = , ϕ
= r ,
DCs DCs = ν ·rspe ·acat −kG/L (CG/s −Cb )·agas (mol·s−1 m−3 ). (1)
where rs and Cs are the specific volume rate and the
The left-hand side represents the differential flow of
concentration at the surface of the film, respectively,
matter in an tore-shaped element of section dz · dr.
D is the diffusion coefficient and L is the characteristic
According to the QSSA, this is equal to the consump-
length (ratio of volume to outer area), and where ϕ

tion in the same element of space given in the right-
makes use of the effective mean rate r which is an
hand side expression. The terms of the left-hand side
experimental value.
represent the longitudinal transport of matter (inter-
Models in thermal catalysis correlate to these mod-
stitial longitudinal rate vL and the radial diffusion
uli the effectiveness of the catalyst, that is the ratio
(effective diffusion constant D). The terms of the right-
η = r/rs . The effectiveness η is equal to or lower than
hand side represent the reactant consumption (where
unity as the concentration within the catalyst is lower
rspe (mol · s−1 ·m−2 ) is the specific superficial rate and
than Cs if internal diffusion interferes. This description
ν the stoichiometric coefficient) and the appearance (in
cannot be directly applied to photocatalysis as a gradi-
the case of oxygen only) through gas-liquid transfer.
ent in LVREA can take place within the catalyst, but a
The balance includes weighing terms: acat the catalyst
numerical treatment has been derived for cylindrical
area, agas the gas-liquid interface area and hup the liquid
pores in the form of an abacus η(ϕ) for various values
hold-up per unit volume. Note that rspe is a function of
of the optical density [16].
the concentrations Cs of reactant and oxygen by the sur-
face catalyst and of the LVREA (modelled separately).
6. REACTOR MASS BALANCE In addition, as seen above, external mass-transfer
in the boundary layer around the particles verifies the
The local specific rate of reaction rspe is a function of
QSSA:
the local bulk concentration Cb and LVREA. The global
mass-balance on the reactants then couples the reac- kext · (Cb − Cs ) = rspe (mol · s−1 m−2 ). (2)
tant disappearance with the mass transfer over the
whole reactor, and leads to the conversion yield. Solving (by a numerical method) the whole system of
Ideal reactors can be classified into three categories: equations of types (1) and (2) for reactant and oxy-
gen, combined with the expression for the rspe includ-
• perfectly-stirred closed reactor (batch reactor), ing the LVREA requires boundary conditions which are
• perfectly-stirred open reactor (CSR), the concentration at the entrance to the reactor and a
zero value of (dCb /dr) on the reactor walls (no flux of
• plug-flow reactor (PFR, or integral reactor). matter).
Vol. 05 Photocatalytic reactors 195

The authors note the importance of the radial dif- through an array of pipes so as to increase the
fusion as the LVREA generates a sharp decrease in the residence time, or through a flat fixed-bed [20] or
rate of the reaction from inner to outer walls. Due to exposure within a tank such as those designed
the complexity of the system model simplifications are for water stations, which can be equipped with
suggested and validated. A first simplification is done impellers designed to ensure a good mixing and
for a highly absorbing medium: the reactor is divided in aerating of the slurry [7, 21],
two zones, a zone by the inner wall where the LVREA is
high and the reaction occurs, supplied by mass transfer • focusing with a mirror (parabolic trough [22])
from the outer second zone. A second simplification for or more elaborate system (Fresnel lenses, holo-
a low absorbing medium is to assume a uniform LVREA. graphic collector) on a reactor of small dimen-
This example deals with a turbulent flow where the fluid sion.
velocity is uniform. This is not the case for a laminar
When using a focusing system, the volume of fluid is
flow where the velocity follows a parabolic profile (slit
reduced, which makes it easier to build, and is also a
flow or falling film reactor). An analysis has been de-
necessity as the whole system (collector + reactor) must
veloped [17] for these cases assuming the annular gap
be placed on a motorised support so as to track the sun.
to be small enough to be treated as a planar system
However, it leads to a high irradiation flux, which may
(i.e. cancelling of the first diffusion term in (1)), which
reduce the quantum yield of degradation. In addition,
showed the advantage of a falling film on a slit flow.
depending on the weather, an important fraction of the
Note that the treatments shown here assume that
sunlight can be diffuse instead of direct, which reduces
only a surface reaction occurs. This is only approximate
the efficiency of the focusing system [7, 22].
as the actual reaction can have a homogeneous part,
An interesting compromise is the Compound
and be partly photolytic if a reactant absorbs the irra-
Parabolic Collector [22] which is fixed, but ensures a
diation light, which requires additional terms of com-
partial focusing and a moderate irradiation flux on the
pound consumption in the right-hand side of (1) [17].
catalyst.

7.2. Artificial light reactors. Artificial light sources

7. GEOMETRY OF THE REACTOR
are on the contrary multidirectional. Two main solution
Two main features determine the design of the reactor: are:

• suspended or immobilised catalyst, • to reflect or focus the emitted light to a reac-

tor [4],
• source of irradiation.
• to wrap the light source with the reactor, such
The obvious advantage of an immobilised catalyst is to as in the coaxial lamp system; this has the addi-
avoid the separation process after the chemical treat- tional advantage that the back-scattering of light
ment, a process which can be an expensive (for the by the catalyst is not a loss as this scattered light
filtration) and time consuming (for sedimentation) con- re-enters the reactor.
sidering the small size of the catalyst crystals or aggre-
gates (0.05 µm to a few µm). However, mass transfer The main artificial sources are mercury lamps:
limitations are more likely to occur within a coat of im-
mobilised catalyst. Various types of support have been • low pressure lamps (254 nm) of high yield “at the
used, made mainly of glass (plate, beads, fibreglass mat) plug” (up to 0.5) of low power (about 30 W/m)
but also paper, cotton, fibres. which require quartz windows,
The source of irradiation can be either natural (so-
• fluorescent lamps (around 365 nm), i.e. low pres-
lar irradiation) or artificial (lamp). The geometry of the
sure lamps equipped with a fluorescent coating,
reactor is strongly related to the source of irradiation,
with a decrease of the emitting power of about
in particular it has to be designed so as to collect the
50% (so-called black-light lamps),
maximum of emitted light so as to reduce the energy
and investment cost. • medium pressure lamp (UV-visible range), higher
in power (about to 3 kW/m) but lower in emission
7.1. Solar reactors. Considering the unidirec-
yield,
tional solar irradiation, the collection of the irradiation
is carried out in two ways [18]: • high-pressure lamp, nearly punctual, with low
part of the emission in the UV range.
• use of a fixed reactor where a large surface of
the solution or suspension is exposed to the High-pressure lamps have a high cost in energy as along
sun: trickling on a flat plate supporting a cata- as UV light is looked for. Medium-pressure lamps have
lyst mesh, flowing a sinuous path [19], flowing a very high power which leads to a low quantum yield
196 M. Bouchy and O. Zahraa Vol. 05

of degradation unless the catalyst is placed at a large of the flow due to centrifugal forces and the building-
enough distance to ensure a low enough irradiation up of successive vortex cells within the annular space
flux, which would be space consuming. According to as shown in a detailed study [28]. Improving the con-
these considerations, fluorescent lamps working with tact between fluid and catalyst can also be obtained
conventional glass vessels are often suggested. by allowing the fluid to pass through a catalyst loaded
An alternative is the distribution of light over a mesh on successive flat or conical supports around the
large area of catalyst by the use of coated optical fi- lamp [29].
bres or hollow tubes [23]. The difficulty of these de- Basically these reactors are built around a single
signs is to collect the maximum amount of light from lamp and large reactors can be obtained by a parallel ar-
the source and to ensure a distribution of irradiation of ray of elementary reactors. The design can be improved
the catalyst along the whole of the light conductor by a by using an array of light sources in a large tank. Hydro-
careful design of the interface loss through refraction. dynamics of such a system is much more complicated
A summary of reactors is presented below, which al- than in the case of cylindrical symmetry. Design of the
though not exhaustive gives an insight into the varia- reactor can be helped by the use of fluid dynamics
tion of designs, some of which have been the object of simulation. Such a study, which is very demanding in
advanced modelling when some others are mainly of an computational equipment, has been demonstrated on
intuitive design. a structure consisting of a cylindrical tank equipped
with seven catalyst-coated hollow tubes acting as light
7.3. Aqueous suspension (slurry). Reactors with
conductors [23]. As a homogeneous “dark” reaction can
suspended catalyst have been the object of fundamen-
also take place, it can be of interest to accommodate
tal studies (e.g. [1, 4, 5, 24]) with the aim of either get-
successive periods of irradiation and thermal evolution
ting true kinetic data or allowing large reactors to be
by a special design of the reactor [26].
designed. Several designs have been studied or sug-
gested. Suspended catalyst has often been used as a 7.5. Gas-phase reactors. Gas-phase reactors are
flow in an annular space [1, 4] around a linear lamp most frequently fixed-bed reactors. Crossing of the cat-
but a thorough study has been dedicated to a falling alyst bed such as coated glasfibre mesh is often envis-
film reactor [24], where a thin film runs freely on the aged as it does not lead to a high pressure drop on the
outer wall within the annular space. If the reaction is one hand and the bed is more resistant to the flow of
fast enough, a radial concentration gradient in the re- fluid on the other. A set of closely spaced fins perpen-
actants will take place, this can be reduced by creating dicular to the lamp can also be used [30]. The catalyst
a turbulent flow by the presence of baffles of various bed can be simply a flat mat supported on a rigid grid
design. A completely different design is the fountain across a pipe with a normal or high incidence irradia-
reactor [25] where a nearly planar horizontal film is ex- tion by a set of lamps [31]. Alternatively a system of
posed to artificial or solar irradiation. These reactors annular geometry can be used where the mesh is of
are meant for water treatment where conversion in the cylindrical shape surrounding the lamp, the gas flow-
reactor is usually very low so that they are coupled with ing through the mesh outwards [32].
a tank with a continuous recirculation of the fluid. Mass An equivalent of the liquid suspension system is
balance for the whole reactor has to take this situation the fluidised bed where the flow of gas through a par-
into account although in the case of a low conversion ticle bed creates a pseudo-liquid state when the flow is
and good stirring of the tank, the reactor is formally strong enough to break the particle packing. This has
analogous to a batch reactor. the advantage of creating a lower pressure drop than
a fixed bed and provides a good mass transfer. In the
7.4. Liquid-phase fixed-bed reactor. Another de-
rotating fluidised bed, the centrifugal forces take the
sign for cylindrical reactors is a fixed-bed reactor where
place of the gravitational forces [32, 33]; this system has
the catalyst is fixed onto a support so as to avoid a sep-
the advantage of having a cylindrical geometry which
aration process. The support can be packed Rashing
is adapted to usual lamps, and allows, by adjusting the
rings [5], fibre mesh whereas an intermediate design
rotating speed, higher flow rates to be used.
between suspended and fixed catalyst uses freely sus-
pended glass beads as catalyst support. Other reactors
use large sized supports such as the inner or outer 8. CONCLUSION
wall of an annular reactor [20]. Confinement of the
catalyst onto a practically two-dimensional surface re- Modelling photocatalytic reactors is of importance in
quires a good mixing of the fluid phase in the annular order to get true intrinsic kinetic parameters and to
space. Creating a turbulent flow by the use of baffles carry out the simulation of industrial-scale reactors so
or foils [26], of a catalyst-coated ridged helix [27], or as to select or to improve the reactor design. Many
by inducing a helicoidal swirl [20] is then important. phenomena are involved in the modelling which re-
An original solution to this problem is also a vortex re- sults in the need for effective parameters and in the
actor where the rotating inner wall induces instability complexity of the solving of the problem by numerical
Vol. 05 Photocatalytic reactors 197

methods. Although a complete treatment appears to [17] D. F. Ollis and C. Turchi, Env. Prog. 9 (1990), 229.
be necessary, simplified models have been suggested [18] J. Blanco and S. Malato, Solar detoxification tech-
to avoid tedious numerical treatments. Applied patents nology, Part B, Chapter 6, UNESCO Publication,
often suggest qualitatively efficient set-up so as to abate 2001.
mass-transfer limitations or make the best use of irradi- [19] B. Volker, M. Müller, D. Bahnemann, D. Weichgrebe,
ation sources. A gap still exists between modelling and and M. Brehm, Reaktoren für die photokatalytische
practical design, which will gradually be reduced with Abwasserreinigung mit Stegmehrfachplatten als
the development of chemical engineering studies in the Solarelementen, EP Patent 0, 738, 686, A1 (1996).
field of photocatalysis. [20] A. Gonzalez-Martin, O. J. Murphy, and C. Salinas,
Photocatalytic oxidation of organics using a
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