0957–5820/05/$30.00+0.

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# 2005 Institution of Chemical Engineers
www.icheme.org/journals Trans IChemE, Part B, May 2005
doi:10.1205/psep.04028 Process Safety and Environmental Protection, 83(B3): 205–216

ENGINEERING DEVELOPMENT OF A PHOTOCATALYTIC

REACTOR FOR WASTE WATER TREATMENT
R. I. BICKLEY
, M. J. SLATER and W-J. WANG
School of Engineering, Design and Technology, University of Bradford, W. Yorks, UK

A
simple design of photocatalytic reactor is proposed based on a study of the use of a
suspension of relatively large titanium dioxide catalyst particles (ca. 10 to 100 mm)
which can be separated from treated waste water using a hydrocyclone. Upward flow
of suspension through an array of ultraviolet lamps and cooling tubes positioned horizontally
is recommended. Flow rate is determined by residence time requirements to suit the kinetics.
This design can be easily scaled up in modular form. The absorption or extinction of light of
appropriate wavelengths by glass, water, pollutant and catalyst particles of different sizes at
various concentrations has been measured to allow determination of catalyst concentration
and suspension thickness required to obtain near total extinction of light. A rate equation is
proposed which shows the part played by the very many factors involved and provides a
new and coherent view of the complex interactions of the variables. The reactor design
methodology is given.

Keywords: photocatalyst; titanium dioxide; water treatment; ultraviolet; reactor design.

INTRODUCTION suspensions; the present work uses much larger catalyst

Photocatalysis, using ultraviolet light and titanium dioxide
catalyst, has gradually attracted more interest as a process
for destruction of toxic organic compounds in waste
waters as environmental awareness and legislation has
increased in recent years. Many studies have been made
on the chemical mechanisms of destruction of specific
chemicals such as pesticides, substituted aromatics, chlori-
nated organics and refractory dyes (Zhang et al., 1994) and
on the photocatalytic behaviour of appropriate materials.
Trace metals can also be removed (Prairie et al., 1993;
Foster et al., 1993; Legrini et al., 1993; Renner, 1996).
Photoreduction of metal ions such as vanadium can be
used to enhance liquid – liquid extraction/separation (Nishi-
hama et al., 2000). It is clear that photocatalysed destruc-
tion of compounds is usually a complex multistaged
chemical process beset with problems of identification of
intermediate products of catalytic oxidation and that only
complete mineralization to mainly carbon dioxide and
water is reasonably certain, even if not economically the
most appropriate goal. It is also the case that titanium
dioxide is the most acceptable and cheap catalytic material
available commercially at the present time.
The previous use of very small catalyst particles (30 nm
to 2 mm) and the difficulties of their recovery from suspen-
sions have led many workers to study reactors with thin
immobilized films of catalyst bonded to surfaces. However,
the performance of films is usually poorer than


Correspondence to: Dr R. I. Bickley, School of Engineering, Design and
Technology, University of Bradford, W. Yorks, BD7 1DP, UK.
E-mail: r.i.bickley@bradford.ac.uk
particles in suspension to solve the recovery problem and
to allow sensible design of large scale equipment.
Photocatalysis has not yet been implemented widely for
water treatment as there are several difficulties to be con-
sidered, which concern the physicochemical limitations and
the engineering aspects of large scale use. The process is not
very efficient in electrical energy consumption terms, not all
organic chemicals respond to catalytic oxidation, reaction
rates are usually slow, and engineering of robust plants capable
of reliable operation with dirty feed waters, sometimes carry-
ing solids or oil drops, requires more thought than is evident
from the current literature on proposed reactor designs.
Some pollutant chemicals pose a serious threat to the
environment, yet are not very amenable to current destruc-
tion processes. So-called advanced oxidation processes
using ozone, hydrogen peroxide, high temperature, cataly-
tic processes, photolysis etc. are needed when biodegrada-
tion processes are insufficient. Studies on many complex
waste waters show that there is no single method suitable
for all cases; all the combinations of ozone/hydrogen per-
oxide/UV photolysis/UV photocatalysis have been tested
in many published examples. All the new oxidation tech-
nologies are more expensive than biological treatment yet
may prove economically feasible in some cases. It is recog-
nized that a series of process steps of different types is
likely to prove most cost-effective, and that processing of
a waste water at source is probably most sensible.
Because of the relatively high cost of electricity, photo-
catalysis should be targeted at refractory pollutants and it
may only be necessary to achieve partial oxidation or
damage to a molecule to render it less toxic. The coupling
of photocatalysis with biological water treatment processes

205
206
is considered sensible (Scott and Ollis, 1995). The destruc-
tion of the toxicity of pollutants is one aim, but COD
reduction is usually also very important. The chemical
pathways of photocatalysis are poorly understood, but
COD reduction is not an immediate consequence, since
carbon dioxide release (or carbonate formation) is needed.
In many of the studies carried out so far, conditions have
not been adequately specified in terms of the spectral range
and intensity of irradiation of catalysts, detailed charac-
terization of catalysts (sometimes ‘home-made’), or reactor
configuration, for example. Many chemicals have been
studied but it is difficult to rationalize most of the available
data to allow comparison of performance. The current work
has been undertaken to document basic rules of light
extinction by suspensions of photocatalysts, to determine
any limits of power input in terms of catalyst activation
or heat transfer which might control performance enhance-
ment, and to consider practical means of catalyst recovery
and recycling. Reactor design requires kinetic information,
in this case on adsorption rates of pollutants by catalysts
and the reaction rates ensuing. A generalized rate equation
is proposed and a method of design of a particular reactor is
set out.
PHOTOCATALYSTS
Photocatalysis is a term first used in about 1910 to
describe the combined effects of electromagnetic radiation
in the presence of a suspended solid upon the course of a
chemical reaction in a liquid phase. This has led to research
on photoactive solids such as titanium dioxide, zinc oxide,
tin oxide and cadmium sulphide. Their use in completely
degrading organic compounds into carbon dioxide and a
mineral acid component (sulphate, chloride, nitrate) then
became of major interest. The anatase form of titanium
dioxide is generally now preferred.
The major engineering problems concern the very small
photocatalyst particle size of typically 0.03 mm, or at lar-
gest 2 mm, used in chemical studies, the low efficiency of
turning electricity into ultraviolet light used for catalyst
activation and the low effectiveness of activation of cata-
lyst. Many chemical studies have been done at rather low
power intensities (kW/m3) and most studies have not
seriously considered the engineering questions of catalyst
recovery or enhancement of photocatalytic rates of reaction
which are usually slow.
Work at Bradford University (Bickley, 1996; Hogg,
1993) has led to the development of a mainly anatase
form of titanium dioxide catalyst of a size range of about
2 to 100 mm with maintained photoactivity induced by a
particular treatment of fine particles (Photox Bradford
catalyst, Table 1). Commercial Degussa VP Aeroperl
P25/20 material of dv50 25 mm size has recently become
available. This size range means that catalyst recovery
Table 1. Photox catalyst particle properties.
Size range, mm dv50 size, mm ag, m2/g Vt, mm/s
10–30 23 37.5 + 0.2
30–60 40 37.0 + 0.2
60–100 67 36.1 + 0.2
Trans IChemE, Part B, Process Safety and Environmental Protection, 2005, 83(B3): 205–216
BICKLEY et al.
from a suspension by hydrocyclone becomes feasible;
recovery of fine particles by filtration or sedimentation
requires large plant size. Periodic operation can be contem-
plated [sunshine plus overnight sedimentation, for example
(Sagawe et al., 2001), or multiplicity of units]. Air flotation
would probably require addition of a flotation reagent.
Some workers immobilize the catalyst in various ways
but this means relatively low areas of exposure of catalyst
per unit volume of water compared to a suspension of
particles.
Titanium dioxide is the safest material to use, being
inert, but there is a dust risk when handled in the dry
state. It is cheap to manufacture since it is used widely in
paint and other preparations.
ULTRAVIOLET LAMPS
Various types of mercury lamp are available operating at
different vapour pressures and temperatures to produce
different emission spectra. The ranges of interest are
UVA 320 –420 nm, UVB 280 –320 nm and UVC
,280 nm; solar radiation falls into the UVA region. It is
known that the radiation of wavelength range around
254 nm (low pressure lamps) can be absorbed directly by
some chemicals so that the process of photolysis can
occur by excitation with these photons. Bacterial disinfec-
tion processes are carried out with such ultraviolet light.
Light of wavelength around 365 nm (medium pressure
lamps) is suitable for photocatalysis with titanium dioxide
which has a band gap or threshold energy equivalent to
413 nm, so requiring smaller wavelengths than this for acti-
vation. Medium pressure lamps give most energy output
above 300 nm, peaking at 365 nm, and falling off above
about 600 nm. It has been shown by Matthews (1992)
that irradiation with 254 nm light can act synergistically
with 365 nm light to improve photocatalytic kinetics
several-fold. The type of lamp used is therefore very sig-
nificant in chemical studies. Medium pressure lamps are
more energy intensive and hotter than low pressure ones
and much of the medium pressure lamp energy is lost as
radiated heat. Lamps rated up to 7 kW (up to about 1 m
long) are commercially available but optimum performance
may be obtained when operated nearer 3 kW. Some lamps
produce ozone in the surrounding air, which can be a
hazard if not appreciated but of benefit if the air containing
ozone is contacted with the polluted water. Since photo-
catalysis requires oxygen (or oxidants) dissolved in
the water a photocatalytic system should include such
water/air contact.
It has been our experience that long (ca. 1 m) lamps
placed vertically can suffer severe problems of electrical
start-up; mercury arc lamps do not obey Ohm’s law. An
argon arc has first to be struck to vaporize mercury by heat-
ing, then a mercury arc can be struck and maintained. If
mercury collects at the base below the electrode after
shut-down, starting the lamp can be difficult. Excessive
cooling of lamps by air or water has also been found to
make start-up difficult. A series of short lamps placed
vertically is not an attractive proposition. However, if the
lamps are placed horizontally then we can have either
0.8 horizontal or vertical flow of water past them.
2.4
7.0
From an engineering point of view it has to be appre-
ciated that Pyrex or similar glass which might be used in
 DEVELOPMENT OF PHOTOCATALYTIC REACTOR FOR WASTE WATER
construction of a plant blocks transmittance of light of
wavelength below 310 nm but quartz is transparent in the
range 160– 600 nm unless specially treated to block UVC
to reduce ozone production. Water is virtually transparent
to light over the wavelength range from 254– 413 nm, but
any chemicals in the water and the particles of catalyst
will absorb or scatter some light. Thus lamps have to be
positioned in air and shine on the polluted water, or be posi-
tioned inside a quartz tube surrounded by polluted water.
The complex geometry of many reactor types requires
calculation of the local rate of light energy absorption; a
system such as an annular reactor with the lamp surrounded
by water, in which all light is emitted reasonably uniformly
along its length, and in which catalyst is well-mixed normal
to the lamp surface is much to be preferred. Many labo-
ratory reactor types are wasteful of light. The scale-up in
axial and radial directions is constrained by light scattering
and the local volumetric light absorption. We have used
Amba AM5663X lamps, medium pressure mercury arcs,
with ozone-free characteristics (UVC blocking) in the
annular reactors described below.
ANNULAR REACTORS WITH HORIZONTAL FLOW
Three annular reactors positioned horizontally were con-
structed, each with a central medium pressure Amba lamp
rated at 3 kW, about 46 cm long, arc length 38 cm,
surrounded by a quartz tube of 30 mm outside diameter.
Each reactor was further surrounded by a Schott Duranw
borosilicate glass tube with annular gaps of 10, 25 and
47 mm, respectively (Wang, 2004). This arrangement
gives reasonably uniform lighting of reactor contents with
no dead spaces. The reactors were then covered with a pro-
tective aluminium shield. Each reactor could be operated
independently. Details are given in Table 2. A batch circu-
lating system was used since it was not expected that a
single pass of polluted water through a short reactor
would give adequate degradation; the system was primarily
designed for data collection.
The system included a mechanically stirred tank with
metered air bubbling through it since photocatalysis can
only be sustained by a ready supply of dissolved oxygen.
Water containing the suspended catalyst was pumped
through a flow meter to any one of the three reactors and
returned to the tank through a single pipe heat exchanger.
Experiments were first carried out to determine the mini-
mum suspension flow velocities for catalyst of three size
ranges. Light extinction measurements were made on the
smallest reactor (type A) using a Bentham Instruments
spectroradiometer with a fibre optical probe set midway
along the lamp and receiving its radiation through a small
circular orifice in the aluminium shield. The UV power
Table 2. Annular reactor dimensions.
Lamp Outer diameter, Inner diameter,
diameter, quartz tube, Duran tube, Gap for water,
Type mm mm mm
A 21 30 50
B 21 30 80
C 21 30 124
Lamp arc length 380 mm, overall length 460 mm.
Trans IChemE, Part B, Process Safety and Environmental Protection, 2005, 83(B3): 205–216
207
output over the wavelength range 365 – 405 nm was found
to be 0.8% of the total electrical power input.
Finally, tests were made on the kinetics of RO16 reactive
orange dye decolourization to assess the effect of power per
unit volume of reactor ranging from about 700–4500 kW/m3
obtained by operating each lamp at about 3 kW with
three different reactor annular volumes.
ULTRAVIOLET LIGHT ABSORPTION AND
EXTINCTION
The Beer –Lambert law is the basis for expressing the
degree of light absorption by pure liquids and solutions.
For suspensions of solid particles light scattering also
plays a part in light extinction; for very small particles,
scattering is substantial and the Beer – Lambert law may
be invalidated. In our case particles are relatively large
and the light extinction profile with depth of suspension
and particle concentration appears to be adequately rep-
resented by the law. The absorption or extinction coeffi-
cients 1 of water, solution and suspension as well as any
glass through which light passes need to be known.
lne ½Io =I ¼ 1Z for single substances (1a)
lne ½Io =I ¼ 1CZ for solutions and suspensions (1b)
For a path length Z the absorption coefficient 1w for
water (with quartz cuvette) was measured in a spectropho-
tometer. Absorption coefficients vary with wavelength of
incident light and data for distilled and tap water are
shown in Figure 1 for the ultraviolet light range. The trans-
mittance data given by Schott for Duran glass were used to
determine 1g.
The process of light extinction for light travelling
through glass then through a suspension of catalyst in pol-
luted water, then possibly exiting through a glass wall can
be described by the equation
lne ½Io =I ¼ S½1i Ci Zi  (2a)
where 1i refers to the glass, water, solution of pollutant and
suspension of catalyst particles. In our case we consider the
mm
10
25
47
Figure 1. Absorption coefficients for tap and distilled water.
208
quartz and air gap to have 100% transmittance at 365 and
405 nm, hence, assuming that Io is the light intensity at
the quartz/water interface and the thickness of water,
solution and suspension are equal
lne ½Io =I ¼ ½1w Z þ 1s Cs Z þ 1c Cc Z þ 1g Zg 
either for a specified wavelength or a range of wavelengths.
The equation is assumed valid for a small annular gap with
near parallel light emission. We are interested in this work
in the amount of power absorbed in the reactor of a given
volume since we consider that the reaction rate is closely
proportional to power absorption. For concentric cylinders
DP ¼ Io Ao  Ie Ae
ffi Io Ao {1  ½exp (  S1i Ci Z) ½1 þ dgap =Ri }
where Ao is the area through which light emanates and Ae
the area of any exit surface.
In many practical cases it is expected that the amount of
light at exit is relatively small since the exponential term is
small and the area correction term then loses significance.
To calculate the amount of power absorbed by the catalyst
we can consider two extreme cases. To simplify pre-
sentation the area correction term [1 þ dgap/Ri] is ignored.
For light passing first through water, then the pollutant
solution,
DP ¼ Io Ao exp½1w Z exp½1s Cs Z
{1  exp½1c Cc Z}
and for light passing through water only before extinction
by catalyst
DP ¼ Io Ao exp½1w Z{1  exp½1c Cc Z}
In equation (3b) the term exp[21sCsZ] varies considerably
during reaction and can be very small if pollutant concen-
tration is large, or 1s very large, yet it will be seen that data
for Cs versus time do not normally show an initial very
slow rate or show strong variation in rate. We have
observed extremely slow kinetics with dinitrotoluene ‘red
liquor’ for which UV light absorbance is very large initially
and during reaction. Photocatalysis is then so slow that in
such cases practical application is uneconomic. In equation
(3c) there is no dependence on the pollutant concentration.
The power absorbed by the catalyst lies somewhere
between the two extreme values. If the products of degra-
dation also absorb UV light strongly then the term
exp[21sCsZ] may be approximately constant. There is
also a possibility that the overall kinetics of the process
are controlled by the consumption of dissolved oxygen by
the catalyst and therefore the process is insensitive to vari-
ations of dye concentration. We have used equation (3a) in
this work which shows much reduced sensitivity to the pol-
lutant concentration changes, but this matter needs more
study.
Dissolved pollutants may absorb light extensively; for
example, we have measured average absorption coefficients
for RO16, a reactive orange dye which has been used in
our photocatalytic studies for ranges of wavelength of
Trans IChemE, Part B, Process Safety and Environmental Protection, 2005, 83(B3): 205–216
BICKLEY et al.
254 – 315 nm and 315 –413 nm obtained by integration of
light intensities measured using a Bentham spectroradi-
ometer in the smallest annular reactor described above
(Table 3). A logarithmic/linear plot of light intensity I
measured outside the borosilicate outer glass tube against
(2b) dye concentration yields a straight line of slope 1s Z
where Z is known. This linearity validates equation (2b)
for our annular geometry.
Finally the absorption and scattering of light by catalyst
particles has to be measured. This was done as for the dye
in the pilot plant by using the Bentham spectroradiometer
under conditions of flow of suspensions of catalysts in
water through a horizontal annular tube. We have used
three size ranges of Photox Bradford catalyst, of size 10 –
30, 30– 60 and 60– 100 mm approximately with mean
sizes dv50 of 23, 40 and 67 mm (measured with a Malvern
(3a) 2600 instrument) and Degussa VP Aeroperl P25/20 of
approximate mean size dv50 25 mm. The variation in cata-
lyst concentration from 0.1– 1 g/L is in a range known
from earlier literature to be appropriate. A logarithmic/
linear plot of light intensity I measured outside the borosi-
licate outer glass tube against catalyst concentration yields
a straight line of slope 1c Z where Z is known. The results
are given in Table 3 and Figure 2.
The photon flux has been said to be inversely dependent
on particle size (Schiavello et al., 1999); at low catalyst
concentration this may be due to the variation of 1c with
inverse of particle size [equation (4)]. The extinction coef-
ficients can be expected to be related to particle size or
specific surface area and this is the case for particles of
the three size ranges used
(3b)
1c ¼ 206(1=dv50 ) þ 2:73 dm2 =g at 365 nm (4a)
1c ¼ 132(1=dv50 ) þ 2:63 dm2 =g at 405 nm (4b)
(3c) (dv50 in mm).
It is expected that virtually all incident light is to be
absorbed by the reactor contents so that Ie  0 which
means finding a combined condition of reactor contents
thickness and suspension concentration to suit. Figure 3
shows the transmittances of the series of components, a
type of plot which can be used for design of a reactor.
Many other workers have used suspensions of Degussa
P25 (30 nm diameter) with which virtually all radiation is
extinguished within a few millimeters for concentrations
of the order of 1 g/L since 1c is about 1200 m2/kg. If the
larger size Photox Bradford catalyst is used near complete
extinction is achieved within a few centimeters for catalyst
concentrations of the order of 1 g/L. The concept of using a
Table 3. Absorption coefficients.
Absorption coefficient 1 at 365 nm 1 at 405 nm
21
Water, m 8.6 8.3
Schott Duran glass, m21 8.9 4.4
RO16 soln., m2/kg 3920 3120
Photox catalyst, m2/kg 10 –30 mm 116 84
30–60 mm 77 57
60–100 mm 60 48
VP Aeroperl, m2/kg 1–80 mm 74 17
 DEVELOPMENT OF PHOTOCATALYTIC REACTOR FOR WASTE WATER
Figure 2. Effect of catalyst concentration on transmitted intensities at
365 nm.
very thin film of suspension, order of 1 mm in thickness, as
a spray or film (Li Puma and Yue, 1999, 2001) on a sloping
or vertical glass surface, irradiated by a lamp has been
developed with P25. However, free film flow is subject to
gravity; film thickness and velocity can be calculated but
gives sensible residence times for reaction only for very
tall reactors, or for some complex arrangement of feeding
many units in a series of shorter reactors.
SUSPENSION AND RECOVERY OF CATALYST
PARTICLES
In a batch reactor, catalyst particles can be kept in sus-
pension by mechanical agitation or by air sparging. In
flow reactors other possibilities have to be considered. A
series of continuous flow stirred tank reactors presents no
problem except that of excessive size compared to plug
flow systems. If the flow of suspension is horizontal then
particle sedimentation is possible and if in an upward direc-
tion then the terminal velocity needs to be known.
Experiments were carried out to check the minimum
horizontal flow velocity (Reynold’s number) needed to
keep particles of three different sizes (of Photox Bradford
catalyst) in suspension in water. Visual observation of
particle deposition was made in three annular reactors
and the results for minimum suspension velocity were
Figure 3. Effect of feed concentration (RO16) on transmittance at
1 g dm23 TiO2(10) concentration.
Trans IChemE, Part B, Process Safety and Environmental Protection, 2005, 83(B3): 205–216
209
adequately correlated with the equation
Res ¼ r dgap Vs =m  104 (5)
suggesting the onset of turbulence as a criterion of
suspension.
The minimum suspension velocity was insensitive to
particle size in the concentration range 0.1 – 1 g/L and at
the horizontal velocities used. The results indicate that in
horizontal annular reactors operated at minimum velocity
of the order of 0.1 m/s, and for anticipated residence
times for photocatalytic reactions of five to 50 minutes or
more for example, reactor lengths will be very long.
While this configuration is not impossible, others need to
be considered. Various baffles were inserted in the annulus
to encourage better suspension of particles but none
showed much improvement. Pulsation could be used but
would add to complexity (Ni et al., 2003).
Suspension upflow velocities must exceed particle term-
inal velocity. The particles are small enough that Stoke’s
law is valid; minimum velocities of about 7 mm/s for
60 – 100 mm size particles would allow sensible residence
times to be achieved in one or two reactors (in series) of
acceptable height of a few meters (Table 1). Downflow is
possible without velocity limitations but water overflow
at the top of the reactor is preferred. A high turn-down
ratio is possible.
Most previous work on suspensions of catalysts has been
done with very small particles (0.03 mm). Catalyst has to be
recovered from the treated water and the system often
suggested is that of sedimentation in a vessel separate
from the reactor. However, terminal velocities are so low
that this is impractical. With particles of 20 mm the term-
inal velocity is about 0.8 mm/s and sedimentation is just
feasible. Great care would be needed to avoid natural
convection currents in a sedimentation tank.
Filtration tests have been carried out on particles of
Photox catalyst of 10– 30 mm (with a superficial filtration
velocity of 1 m3/m2 h for 0.75 g/L catalyst) and the calcu-
lated size of filtration units is again feasible but such units
are expensive and not attractive. Membrane filtration is also
possible but subject to low fluxes and potential problems
with fouling. Our preferred solution to the problem of cat-
alyst recovery is to use larger size catalyst materials and a
hydrocyclone. A hydrocyclone can remove titanium di-
oxide particles down to about 2 mm; a high pressure
slurry pump (a Monopump) is required to feed a single
cyclone of about 10 mm diameter and about 15 cm high
at a flow rate of 1 m3/h (Richard Mozley Ltd.). Such
systems are very robust, being much used in hydrometal-
lurgical plants for ore processing.
THE EXPOSED SURFACE AREA OF CATALYST
PARTICLES
Although the interior surface area of particles can be
measured by the BET method it is only a very small
depth of exposed surface which can be activated by UV
light. The requirement for exposure of a very large surface
area of catalyst to UV light to enhance poor kinetics has
been shown by many previous workers, hence the use of
Degussa P25 catalyst and similar materials with particle
210 BICKLEY et al.

size of about 0.03 mm and area of ca. 40 m2/g. The surface KINETICS OF PHOTOCATALYSIS
area measured by BET Micromeritics ASAP2010 and
A detailed rate equation is necessary in appreciating the
nitrogen adsorbate was about 37 m2/g for each particle
relative importance of the many factors involved. It is
size range of Photox catalyst. Density was measured as
known that adsorption of pollutant on the catalyst is a prob-
3840 + 110 kg/m3 (Helium pycnometer 1305s). The
able rapid first step and that overall first and zero order
extinction coefficient for light of fine Degussa P25 particles
reactions are often observed (e.g., Chester et al., 1993).
in suspension is of the order of 10 times that of particles of
The concentration of dissolved oxygen is also known to
about 10 mm so the thickness of suspension required to
be important but in this present case saturation is supposed
extinguish virtually all incident light is 10 times smaller
(Bangum and Adesina, 1998). This matter was checked
than with larger particles. Specific outer surface area of
with the use of a dissolved oxygen meter. Kinetic data
uniform spherical particles in the reactor is given by
are impossible to place in perspective in many previous
studies because they have not been related to power input
av ¼ 6v=dp (m2 =m3 ) (6a) and various lamp types have been used.
2
Initial rates of reaction have been found in some cases to
ag ¼ 6=rdp (m =g) (6b) be proportional to catalyst concentration at low values and
become nearly independent of concentration at higher
where v is the volume fraction in suspension and dp the values, depending on reactor geometry and working
Sauter mean particle size. conditions (Reutergardh and Iangphasuk, 1997; Herrmann,
If we use larger particles to solve the recovery problem 1999; Nam et al., 2002; Chen and Ray, 1998, 1999).
the much lower outer specific surface area can be compen- Terzian and Serpone (1995) have shown that the relation-
sated partially by using higher concentrations of particles ship between initial rate and catalyst concentration can be
and deeper suspensions to achieve the same extent of fitted by a Langmuir type of equation. In many cases an
light absorption. A proprietary technique of making larger optimum catalyst concentration has been noted at concen-
particles while maintaining titanium dioxide activity has trations sometimes below and sometimes far in excess of
been developed; this Photox catalyst now allows a different that required for near complete light extinction (Goncalves
approach to reactor design. The new Degussa VP Aeroperl et al., 1999; Wang and Adesina, 1997; Bangum and
P25/20 catalyst of larger size also has good reactivity and Adesina, 1998; Martin et al., 1999; Li Puma and Yue,
is suitable for the system proposed in this work. 1999; Serpone, 1997; Dijkstra et al., 2001). Various reasons
for this behaviour have been offered without much convic-
tion or quantification and the question needs to be resolved
to assist design work.
Our own work also provides an example of the rate
FIXED CATALYST SYSTEMS improving as catalyst concentration increases, then falling
slowly, using Degussa P25 catalyst degrading pure isopro-
If particles of catalysts are bonded to an immobilized
panol in a 250 mL batch reactor (Hogg, 1993). The catalyst
surface to avoid the problem of catalyst recovery pollutants
concentration at which the rate reaches a maximum is much
have to be transported to this surface by convective motion
greater than that required for near complete light extinction.
and molecular diffusion. If very high intensities of
In contrast, for Drimarene Brilliant Blue dye destruction in
irradiation are used rate coefficients can be similar to
a 25 L batch stirred tank reactor (Photox catalyst) no
those obtained in reactors with catalyst suspension
significant dependence on catalyst concentration was
(Zhang et al., 1994). Chester et al. (1993) state that rates
found for the catalyst concentrations used (25, 75 and
of degradation (as distinct from the rate coefficient) for
250 mg/L) (Figure 4).
catalyst supported on a membrane are less than for a sus-
pension reactor. Although data are sparse and difficult to
compare, the intensive rate (or productivity, g/L/s) of
suspension reactors seems larger than that of fixed catalyst
reactors (see Matthews, 1987). The rate coefficients for
bonded catalysts can be interpreted as diffusive mass trans-
fer coefficients (Turchi and Ollis, 1988). If laminar flow is
used in an immobilized catalyst reactor diffusion distances
may be much larger than in suspension reactors and mass
transfer limitations can be incurred. The spinning disc reac-
tor (Yatmaz et al., 2001) or surfaces using coated glass
beads (Franke and Franke, 1999) can help overcome this
problem by film thinning. Mass transfer resistance is negli-
gible for suspension reactors according to Ollis et al.
(1989), Chen et al. (1999) and Lea and Adesina (1999).
The distance between particles in a suspension is about
12 times the particle diameter for 1 g/L catalyst (and
26 times for 0.1 g/L) so even with the relatively large
particles used in this work diffusion distances are very
small compared to a fixed catalyst system unless turbulence
in the bulk fluid is induced in a fixed catalyst system. Figure 4. Degradation of Blue dye in 25 L batch reactor.

Trans IChemE, Part B, Process Safety and Environmental Protection, 2005, 83(B3): 205–216
 DEVELOPMENT OF PHOTOCATALYTIC REACTOR FOR WASTE WATER
The initial rate has been found linearly proportional to
radiant flux Io but above a certain level (about 50 W/m2
but very variable) the rate shows lesser dependency
(Esplugas et al., 1987; Mills et al., 1993; Dillert et al.,
1995; Augugliaro et al., 1995; Terzian and Serpone, 1995;
Martin et al., 1996; Reutergardh et al., 1997; Herrmann,
1999; Chen and Ray, 1998). It is possible that disadvanta-
geous electron/hole pair recombination becomes more
important at higher light intensities. Many authors suggest
that the dependence of rate on light intensity is linear at
low intensity then apparently of 0.5 order at higher inten-
sity. The transition region varies. There may also be an
upper limit imposed by the mass transfer rate (Ollis
et al., 1991). The data of Terzian and Serpone (1995)
show clearly that these two regions of approximate propor-
tionality to Io and I0.5
o are followed by a plateau of constant
maximum rate. The data of Egerton and King (see Mills
et al., 1993) also show such behaviour over five decades
of light intensity. To explain these observations we
consider that the rate is proportional to light intensity but
with an efficiency of conversion of light energy to
electron/hole pairs which decreases as Io increases.
The published data therefore show a wide variety of
characteristics of plots of initial rate or rate coefficient
against catalyst concentration and light intensity. The plot
of rate against catalyst concentration may show a sharp
rise to a peak followed by a slow decline; it may show
a rise to a constant maximum value; it may show a sharp
rise followed by a more gradual rise. The peak or plateau
region does not necessarily coincide with the condition of
near maximum light extinction. It is notable that few
authors question the concentration of catalyst to use in a
suspension reactor; most investigations use an arbitrary
level as used by others. In most cases it seems that the con-
centration used is very far in excess of the level required
for near total light extinction. The dependence of rate on
light intensity should be considered a smooth function simi-
lar in shape to that of a Langmuir adsorption isotherm,
reflecting the manner in which the net concentration
of charged species can be determined by competitive
processes.
A NEW RATE EQUATION
For a volume of well-mixed suspension V containing a
mass M of catalyst with specific outer surface ag (m2/g)
and surface concentration of adsorbed pollutants on the
particles q, the rate of reaction is suggested to depend upon
2
(1) The surface area of catalyst in volume V, i.e., M ag (m )
(2) Concentration of adsorbed pollutant on the catalyst at
any time in volume V, which is q (kg pollutant/m2
catalyst). We assume the Langmuir description of equi-
librium adsorption of pollutant as usually done (Turchi
and Ollis, 1990; Matthews, 1988; Kumar and Davis,
1997) but modified to make it more flexible
q=Q ¼ KCsm =½1 þ KCsm  (7)
and that adsorption equilibrium is achieved very
rapidly compared to the photocatalytic rate of reaction.
(3) Concentration of electron/hole pairs on the catalyst, CE
(kg pairs/m2 catalyst). This concentration is proposed
Trans IChemE, Part B, Process Safety and Environmental Protection, 2005, 83(B3): 205–216
211
to be some function of power absorbed in the volume
V by the particles alone or the whole suspension per
unit of outer surface area of particles (a surface concen-
tration of light on the catalyst, Cl) where for the whole
suspension
Cl ¼ DP=Mag
¼ Io Ao {1  exp½S(1i Ci Z)}=VCc ag (8)
We relate the concentration of electron/hole pairs to this
light concentration Cl using
CE ¼ Kl (Cl w)p (9)
using an exponent p to allow for nonlinear imperfections
in the conversion process. An analysis of the process of
converting incident light energy into electron/hole pairs
leads to an expression for a factor w of conversion which
decreases as light intensity increases because of the increas-
ing extent of recombination of electrons and holes as photo-
electronic processes progressively take place deeper within
the particle sub-surface region., (private communication,
Bickley, 2003), where
w ¼ kp exp½b={1 þ kp exp½b} (10a)
and for the whole suspension
b ¼ aIo Ao {1  exp½S(1i Ci Z)}=VCc ag (10b)
We can write a balance for behaviour in the bulk solution
and for the surface of the catalyst as
V dC=dt ¼ ko Mag qCE (11)
or
dC=dt ¼ ko Cc ag qCE (12)
so by substituting for q and CE and lumping coefficients
we obtain
dC=dt ¼ kr Cc ag {KCsm =½1 þ KCsm }
{Io Ao ½1  exp (  S1i Ci Z)=VCc ag }p
{kp exp½b=½1 þ kp exp ( b)}p (13)
We use the equation (13) using midrange values of Cs in
calculating light extinction. Using equation (13) it is seen
that the extinction of light is nearly complete in our work
and is little affected by variation in Cs. The light conversion
factor w varies strongly with Cs only at high light intensity.
The rate data we have obtained seem adequately fitted
using the equations based on light extinction by the
whole suspension; it is considered that the products of
dye degradation may also absorb light strongly so that
very large changes in reaction rate are not incurred. For
systems in which the light is strongly absorbed by the pol-
lutant, but not degradation products, this is likely not to be
the case.
212 BICKLEY et al.
For the dependence of initial rate on catalyst concen-
tration alone, calculations show that when p , 1 the rate
rises quickly at very low concentrations then rises more
gradually; when p ¼ 1 the rate rises to a plateau and
when p . 1 the rate rises quickly to a peak and then
decreases slowly. All these cases have been found in prac-
tice. For the dependence of initial rate on light intensity
alone, approximations can be made to Io or Io0.5 but this is
not very helpful. The value of exponent p is expected to
be near 1 to accord with data obtained at low light levels.
The dependence on particle diameter alone (for near com-
plete light extinction since 1c varies with dp) can also be
calculated.
The rate equation can be expressed more simply for a
given reactor and fixed operating conditions as
dC=dt ¼ kKCsm =½1 þ KCsm  (14)
A calculation procedure was developed which uses the rate
equation (14) for the time spent in the plug flow annular
reactor together with nonreactive time in the mixing tank
in the pilot plant. The results agree with the equations of
Wolfrum and Turchi (1992) after a few residence times
in the mixing tank. Experimental data were fitted using
the Solver routine in MS Excel but a large number of
data points are needed to obtain values of k, K and m
with good statistical certainty. The k values obtained do
not take into account any variation of light absorption
changes with time, and therefore Cs, as dye is degraded.
It is assumed that immediately the catalyst contacts the
water an equilibrium is achieved between pollutant in
solution and on the catalyst so that there is a sudden
decrease in concentration—a concentration jump (or a
marked reduction within the first few minutes of contact).
The effect is clearly seen in the dye destruction data
given by Tang and An (1995) and our data for blue dye
(Figure 4). A mass balance gives the size of the jump to
initial conditions:
V(Cf  Ce ) ¼ Mag (qe  0) (15)
and qe is in equilibrium with Ce as given by equation (7). If
KCsm  1 then
(Cf  Ce ) ¼ Cc ag Q (16a)
and if KCsm  1 then
(Cf  Ce ) ¼ Cc ag Q(KCfm ) (16b)
and the jump is much smaller.
Integration between Ce at time zero and C for time t for a
batch stirred tank or a plug flow continuous reactor with
concentration of pollutant in the feed Cf gives for the
simple case of m ¼ 1
½1=kK lne {Ce =C} þ ½1=k(Ce  C) ¼ t ¼ V=F (17a)
which represents a combined first order plus a zero order
rate equation. According to this model, if the adsorption
on the catalyst is highly favourable then a concentration
jump proportional to catalyst concentration is followed by
Trans IChemE, Part B, Process Safety and Environmental Protection, 2005, 83(B3): 205–216
a reaction of zero order. This is followed by a first order
process as C grows smaller and the ratio {Ce/C} grows
larger. If KC  1 then a first order is favoured throughout
with negligible concentration jump. In the case that m = 1
then
(1=k)½(Ce1m  C1m )=(1  m)K
þ (1=k)½Ce  C ¼ t (17b)
In our work we have measured K and m in separate exper-
iments on adsorption equilibrium in the dark. For RO16 dye
and TiO2(10) m ¼ 1, K ¼ 0.0012 dm3/mg and Q.ag ¼
120.5 mg/g (Figure 5). The values for the larger size fractions
are very similar. For VP Aeroperl m ¼ 1, K ¼ 0.0011dm3/mg
and Q.ag ¼ 222 mg/g. For 2-chlorophenol adsorption on VP
Aeroperl we find m ¼ 1, K ¼ 0.1228 mM21 and Q.ag ¼
1.274 mmol/g. So in these several cases the Langmuir
isotherm describes data very well. If K varies with Io
(Xu and Langford, 2000) then it is conceivable that measure-
ments in different reactor types can give reaction rates of
different order. Care must be taken not to use invalid data
for scale-up to a different reactor type.
Experimental data from our own work are shown here
(Figures 4, 6) for a low powered 25 L batch stirred cell
reactor with Drimarene Brilliant Blue-4BL dye at various
low Photox catalyst concentrations and for a low powered
250 mL batch reactor (Hogg, 1993) for 2-chlorophenol
using P25 at 0.75 g/L. In the case of the dye a zero-order
process with concentration jumps fits well, although the
dependence of the jump on catalyst concentration is not
strong. Initial zero-order kinetics are found with a possible
concentration jump in one case for the 2-chlorophenol.
Figure 7 shows data for RO16 dye for three sizes of
Photox catalyst in the smallest annular reactor A (with a
concentration jump). Equation (14) was used to find that
m ¼ 1, using the K value already measured gives a good
fit. The rate coefficient k variation with ag for these data
is then well-modelled using the new rate equation
(Figure 8); the small number of data points does not
allow accurate determination of all the unknown coeffi-
cients but a good fit can be obtained with the values
chosen; kp was varied between 0.1 and 10 with little
effect on the other parameters. The exponent p ¼ 1, so
destruction of this dye appears to follow a simple rate pro-
cess, perhaps because colour removal depends on a first
Figure 5. Langmuir adsorption isotherm for TiO2(10)/RO16.
 DEVELOPMENT OF PHOTOCATALYTIC REACTOR FOR WASTE WATER
Figure 6. Degradation of 2-CP.
simple step of molecular cleavage. The illumination does
not appear to have changed the adsorption parameters.
An experiment with no catalyst showed that there was no
detectable photolysis because of the absence of UVC.
In all cases it must be remembered that the degradation
chemistry is complex and multicomponent so a simple
description of kinetics can only be approximate.
POWER INPUTS AND HEAT REMOVAL
To maximize rates of reaction the power input needs to
be high, the actual input to be decided by cost calculations.
Unfortunately, most of the electrical energy is dissipated
(radiated) as heat. The power input per unit volume of reac-
tor is often very low in laboratory studies but values near
2000 kW/m3 have been used in a few cases. According
to flow rate of water and residence time in a continuous
flow reactor the water will rise to a particular temperature.
In some cases temperatures could approach boiling point,
so limiting operating conditions unless cooling tubes are
provided in the reactor. In finding a compromise design
solution to a problem the possible need for heat removal
must not be forgotten. The recovery of heat from treated
water should be done to reduce site costs elsewhere.
Figure 7. Decolourization kinetics of RO16 for three sizes of Photox
catalyst in annular reactor A (R1-R3).
Trans IChemE, Part B, Process Safety and Environmental Protection, 2005, 83(B3): 205–216
213
Figure 8. Effect of particle specific outer surface area on k in reactor A.
Data for RO16 were obtained for the three annular reac-
tors (Figure 9). The rate of destruction of dye RO16 with
1 g/L Photox catalyst (dv50 67 mm) with the three sizes
of annular reactor showed that the rate coefficient k
increased linearly as total input power per unit volume
increased but levelled off at near 3000 kW/m3 (as found
also by Zhang et al., 1994). Figure 10 shows the variation
of the rate coefficient with UV power absorbed which is
well-modelled with the same values of parameters kr, a, p
and kp as for dependence on ag.
EFFECT OF CATALYST TYPE
Figure 11 shows data comparing Photox catalyst (dv50
23 mm) with similar size VP Aeroperl P25/20 used in the
smallest annular reactor A. The VP catalyst shows a
value of m other than the value of 1.0 measured for adsorp-
tion in dark conditions and there is a difference in reaction
order between the two catalysts. Xu and Langford (2000)
have noted this effect.
REACTOR WITH UPWARDS FLOW
Experience with the annular reactors has led to a propo-
sal for a design of a system suitable for industrial use. An
Figure 9. Decolourization kinetics of RO16 for three levels of energy input
(R3 –R5).
214 BICKLEY et al.
Figure 10. Effect of UV power densities on k in the annular reactors.
efficient reactor requires complete immersion of the lamps
(Esplugas et al., 1987) and good mixing of the catalyst sus-
pension in the direction normal to the lamp surface (Ollis
and Turchi, 1990).
It is proposed to have upwards flow in a full-scale reactor
with a rectangular cross-section of about 50 cm by 10 cm
with 3 kW lamps horizontally disposed at intervals within
quartz tubes, with a separation distance of 10 – 30 cm,
giving a maximum power density of about 600 kW/m3.
Sufficient space for cleaning the quartz tubes surrounding
lamps is required; mechanical cleaning devices have been
developed. Water containing iron compounds tends to
coat the tubes (Zappi et al., 1990); acidification can be
used to keep iron in solution. Horizontal cooling tubes
are required. Water flow is upwards at a velocity giving a
satisfactory residence time which, in turn, depends on the
reactor height and number of lamps used. Flows at very
low velocities which are nominally laminar can be dis-
turbed by baffles, any cooling tubes and the lamp tubes to
flatten the velocity profile by radial mixing and approach
plug flow. One or more identical modular units several
meters high may be needed. The allowable flow rates will
be determined by the kinetics but with a suggested super-
ficial velocity of say 1 mm/s in a unit 6 m high, we can
obtain a residence time of 100 minutes which is considered
sufficient for photocatalytic processing of a variety of
Figure 11. Decolourization kinetics of RO16 for different catalysts in
annular reactor A.
Trans IChemE, Part B, Process Safety and Environmental Protection, 2005, 83(B3): 205–216
serious pollutants. The flow rate at 5 mm/s is about
1 m3/h per module. Pollutants which are more rapidly
degraded allow higher flow rates; multiple modules may
be required and treatment at source of low flow rate streams
is desirable.
From equations (13) and (17a,b) it is seen that a continu-
ous plug flow reactor volume is expected to be inversely
proportional to Io Ao/V (power per unit volume kW/m3).
As power per unit volume is increased, the reactor
volume decreases and lamps become closer together, poss-
ibly making construction and cleaning more expensive and
difficult. However, the number of lamps remains constant
(other factors being fixed) as volume decreases so capital
costs are little affected since the major component of
capital cost lies in the lamps and transformers rather than
the volume of the reactor. A sensible lower limit of lamp
spacing of 10 cm is suggested for an industrial design,
giving an upper limit of power per unit volume of about
600 kW/m3 for a catalyst suspension reactor of the type
proposed.
REACTOR DESIGN PROCEDURE
(1) The absorption coefficient for the polluted water
needs to be measured (including any turbidity which
will reduce performance). If the absorption coefficient
1sCs of the polluted water is much larger than typical
values of 1cCc the catalyst is obscured and reaction
rates may be very low.
(2) A plot of transmittance against suspension thickness
for the chosen catalyst (as Figure 3) needs to be made.
(3) A thickness of suspension and catalyst concentration
giving a specified degree of light extinction of say
95% are chosen as a first estimate.
(4) A box shape for one lamp is assumed with length of
50 cm (lamp length) and width and depth of the
chosen suspension thickness. The box volume is
calculated.
(5) Calculate power per unit volume assuming lamp
power of 3 kW in the box volume.
(6) Batch circulation experiments with one or more lamps
need to be made initially. The catalyst concentration
should be varied to determine an optimum value.
(7) Assume linearity of the plot of rate coefficient against
total power per unit volume. Choose a high power per
unit volume (maximum 600 kW/m3) and read a rate
coefficient value. Calculate the volume of the reactor
for specified degree of destruction of the pollutant
[equation (17a,b)].
(8) Calculate power from the assumed power/unit
volume and number of 3 kW lamps (i.e., number of
boxes), equal to the ratio of reactor volume and box
volume.
(9) Estimate capital and running costs and cost per m3 of
treated water.
(10) Repeat calculations to find a satisfactory design
solution.
CONCLUSIONS
To encourage industrial use of photocatalytic reactors it
is necessary to find a compromise between many
 DEVELOPMENT OF PHOTOCATALYTIC REACTOR FOR WASTE WATER
parameters to achieve a practical, robust, inherently safe,
controllable system able to cope with flow variations,
with no fine tolerances in mechanical parts, and which is
easy to scale-up. The new rate equation proposed demon-
strates the complex relationship between the many vari-
ables and should be helpful in the search for an optimum
design and in understanding experimental results. More
study is required to understand how pollutant solutions
which strongly absorb UV light affect the kinetics.
It appears feasible to design a flexible modular photo-
catalytic reactor with minimal hydrodynamic restrictions
or sensitivities to upsets and easy access for maintenance
of lamps and cleaning of surfaces. A flow rate per
module of the order of 1 m3/h is expected. A different
lamp type (e.g., low pressure) could be used if required
to obtain photolysis as well as photocatalysis or to find a
more economical design. By using larger particle size
catalyst it becomes possible to use robust hydrocyclones
for catalyst recovery, a more acceptable solution than sedi-
mentation or filtration. Although catalyst reactivity is lower
than with very fine particles, the catalyst is cheap and the
use of high power input with near total light extinction is
expected to allow processing of refractory pollutants in a
plant of sensible size. Although use of electricity is ineffi-
cient and expensive, the proposed plant design and con-
struction is not demanding and overall costs may prove
competitive with other advanced oxidation processes
which have been tried in the search for methods of destruc-
tion of toxic chemicals in water. Photocatalysis may find a
niche in treating chemicals at low concentration which do
not biodegrade. Partial attack to yield biodegradable pro-
ducts rather than complete mineralization may prove
most economic but this depends on legislative targets or
on charges made on the basis of COD of effluents
(Etheridge and Leroff, 2002).
NOMENCLATURE
a coefficient in equation (10b), m2/kW
ag specific outer surface area of particle, m2/g
av specific outer surface area of particle, m2/m3
Ae surface area of annulus at exit of light, m2
Ao surface area of annulus at entry of light, m2
C, Cs pollutant concentration, kg/m3
Cc catalyst concentration, kg/m3
CE surface concentration of electron/holes, kg pairs/m2 catalyst
Ce pollutant concentration after concentration jump, kg/m3
Cf pollutant concentration in feed, kg/m3
Cl surface concentration of light, kW/m2
dgap gap between glass tubes, m
dp Sauter mean particle diameter, m
dv50 volume median diameter of particles, m
F flow rate of solution, m3/s
I radiation intensity, W/m2
Ie radiation intensity at reactor exit surface, W/m2
Io radiation intensity at quartz/water interface, W/m2
k rate coefficient, kg/s m3
ko coefficient in equation (11), kg pairs. g cat/kg cat m2 s
kp coefficient in equation (10a)
kr rate coefficient, kg/s kW (for p ¼ 1)
K adsorption equilibrium coefficient, (m3/kg)m
Kl coefficient in equation (9)
m exponent
M mass of catalyst, kg
ns pollutant concentration on catalyst, kg/kg catalyst
p exponent
P power, kW
q surface concentration of pollutant on catalyst, kg/m2
Trans IChemE, Part B, Process Safety and Environmental Protection, 2005, 83(B3): 205–216
215
Q maximum surface concentration of pollutant on catalyst,
kg/m2
Res Reynolds number
Ri radius of quartz tube surrounding the lamp, m
T transmittance
t time, s
tuv time of exposure in reactor, s
V reactor volume, m3
Vs minimum suspension velocity, m/s
Vt terminal velocity, m/s
v volume fraction of particles
Z suspension thickness, m
Greek Symbols
b coefficient
1 absorption coefficient, m2/kg or m21
w efficiency
m viscosity, kg/ms
r density, kg/m3
l wavelength, nm
Subscripts
c catalyst in suspension
e equilibrium
f feed
g glass
s solution
w water
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ACKNOWLEDGEMENTS
Much of the work was funded by an EPSRC Grant No. GR/N26029/01
which is gratefully acknowledged. Degussa AG supplied samples of
Degussa VP for which we express thanks. Some data were obtained by
R. Williams on behalf of Photox Bradford Ltd.
The manuscript was received 5 February 2004 and accepted for
publication after revision 30 November 2004.