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A semiconductor photocatalytic process has been studied extensively in recent years because of
its intriguing advantages in environmental remediation. In this study, a two-phase swirl-flow
monolithic-type reactor is used to study the kinetics of photocatalytic degradation of Eosin B
for two different operating configurations: substrate-to-catalyst and liquid-to-catalyst illumination modes. True kinetic rate constants were determined as a function of the light intensity and
catalyst layer thickness after correcting for mass-transfer limitation. In addition, the effects of
several other parameters such as pH, dissolved oxygen, and temperature were examined. This
new reactor appears to be an attractive choice for kinetic studies of heterogeneous photocatalysis.
Introduction
Heterogeneous photocatalysis has received considerable attention in recent years as a viable treatment
technology for handling industrial effluents and contaminated drinking water. This is evident from the
numerous review papers that have been devoted to this
field.1-13 The process couples low-energy ultraviolet
light with semiconductors acting as photocatalysts. In
this process, electron-hole pairs that are generated by
the band-gap excitation carry out in situ degradation
of toxic pollutants. The holes act as powerful oxidants
to oxidize toxic organic compounds, while electrons can
reduce toxic metal ions to metals, which can subsequently be recovered by solvent extraction.14 Photocatalytic degradation offers certain advantages over the
traditional water treatment methods. Complete destruction of most contaminants is possible without the need
of additional oxidizing chemicals such as hydrogen
peroxide or ozone. Degussa P25 TiO2 is widely used as
the photocatalyst, which requires UV-A light ( < 380
nm) of intensity 1-5 W/m2 for photoexcitation. The
catalyst is cheap and can also be activated with sunlight.11
TiO2 catalyst has been used in two forms: freely
suspended in an aqueous solution and immobilized onto
a rigid inert surface. In the former case, a high ratio of
illuminated catalyst surface area to the effective reactor
volume can be achieved for a small, well-designed
photocatalytic reactor,15 and almost no mass-transfer
limitation exists because the diffusional distance is very
small, resulting from the use of ultrafine (<30 nm)
catalyst particles.16 In large-scale applications, however,
the catalyst particles must be filtered prior to the
discharge of the treated water, even though TiO2 is
harmless to the environment. Hence, a liquid-solid
separator must follow the slurry reactor. The installation and operation of such a separator will raise the cost
of the overall process because the separation of the
ultrafine catalyst particles is a slow and expensive
process. Besides, the penetration depth of the UV light
is limited because of the strong absorption by TiO2 and
* To whom correspondence should be addressed. Fax: +65
6779 1936. E-mail: cheakr@nus.edu.sg.
Ind. Eng. Chem. Res., Vol. 42, No. 24, 2003 6021
need of separation for postprocess treatment. Experiments are performed to determine the various rate
constants. Experiments are also conducted to study the
effect of light intensity and catalyst layer thickness on
the reaction rate constants for two different operating
modes, viz., when light falls directly on the catalyst
[substrate-catalyst (SC) illumination] film and when
light has to travel through the absorbing heterogeneous
medium to activate the catalyst [liquid-catalyst (LC)
illumination]. As is evident for most fixed-bed catalyst
systems, mass-transfer limitations do exist. These are
measured, and the results are corrected to obtain pure
kinetic data. Fundamental experimental macrokinetic
data on photocatalytic oxidation of Eosin B are investigated under conditions that are relevant for evaluation
of the design of other reactors.
Experimental Details
Materials. Eosin B (C20H6Br2N2Na2O9, acid red 91,
CI 45400, MW 624.1), a xanthene dye widely used as a
biological stain, was provided by Sigma Co. Eosin B is
widely used to estimate a wide range of proteins because
in acidic solution Eosin B binds to proteins and absorption of the protein-dye complex around 536-544 nm
is proportional to the concentration of the proteins. The
stain is harmful if swallowed, inhaled, or absorbed
through skin. Some researchers have tried to remove it
by adsorption, but no one has attempted for complete
degradation. This is an excellent model component for
the characterization of a photocatalytic reactor, and the
dye is reactive only in the presence of both TiO2 and
UV light and is biologically not degradable.
Degussa P25 catalyst provided by Degussa Co. (Germany) was used throughout this work without further
modification. Its main physical data are as follows:
Brunauer-Emmett-Teller surface area 55 ( 15 m2/g,
average primary particle size around 30 nm, purity
above 97%, and anatase-to-rutile ratio 80:20. Nitric acid
(65 wt %) and sodium hydroxide (98%) are from Baker
6022 Ind. Eng. Chem. Res., Vol. 42, No. 24, 2003
Ind. Eng. Chem. Res., Vol. 42, No. 24, 2003 6023
Before the start of the photocatalytic reactions, experiments were conducted to investigate whether there
is any direct photolysis (in the presence of light but in
the absence of any catalyst). It was observed that no
direct photolysis takes place for Eosin B. When experiments were conducted in the presence of catalyst but
in the absence of light (dark reaction), a small decrease
in the concentration of Eosin B was observed because
of adsorption of the model compound onto the catalyst
surface, which reached an equilibrium value within 900
s. Hence, before the light was turned on, it was always
ensured that adsorption equilibrium was reached. Therefore, degradation of Eosin B in the presence of light and
catalyst observed is entirely due to photocatalysis.
Effect of the Initial pH. The pH of the reaction
medium has a significant effect on the surface properties
of the TiO2 catalyst, which include the surface charge
of the particles, the size of the aggregation of the
catalyst particles it forms, and the band edge position
of TiO2. Because a photocatalytic degradation reaction
takes place on the surface of the catalyst, the photocatalytic reaction, in general, is pH-dependent although
the rate varies by less than 1 order of magnitude
between pH 2 and 12 (2, 6). The point of zero charge
(pHzpc) for Degussa P25 TiO2 is at a pH equal to 7.2.
The amount of positive charges on the TiO2 surface
decreases with increasing pH and reaches zero at pHzpc.
Therefore, pH significantly affects the adsorptiondesorption properties of the model compounds on the
Figure 6. Calculation of the adsorption rate constant from a dark reaction. Experimental conditions: Re ) 141, VL ) 2.4 10-4 m3, w
) 5.2 10-3 kg/m2, T ) 303 K, catalyst on the bottom plate.
6024 Ind. Eng. Chem. Res., Vol. 42, No. 24, 2003
Cads )
NKCeq
1 + KCeq
(1)
rrxn )
[ ][ ]
VL
dCb
krKCs
)
VR
dt
1 + KCs
(2)
Ind. Eng. Chem. Res., Vol. 42, No. 24, 2003 6025
Figure 8. Effect of the catalyst layer thickness on the photocatalytic degradation rate of Eosin B. Experimental conditions: C0 ) 16
mmol/m3, Q ) 5 10-6 m3/s, I ) 33 W/m2, VL ) 2.4 10-4 m3, T ) 303 K, pO2 ) 60.8 kPa, natural pH.
6026 Ind. Eng. Chem. Res., Vol. 42, No. 24, 2003
Figure 9. Photocatalytic degradation of Eosin B at different initial concentrations. Experimental conditions: SC illumination, Q ) 5.0
10-6 m3/s, I ) 33 W/m2, w ) 5.2 10-3 kg/m2, VL ) 2.4 10-4 m3, T ) 303 K, pO2 ) 60.8 kPa, natural pH.
Figure 10. Effect of the circulation rate on the photocatalytic degradation rate of Eosin B. Experimental conditions: SC illumination,
C0 ) 16 mmol/m3, I ) 33 W/m2, w ) 5.2 10-3 kg/m2, VL ) 2.4 10-4 m3, T ) 303 K, pO2 ) 60.8 kPa, natural pH.
parameter in any process water treatment and, therefore, it is essential to examine the effect of the initial
concentration. However, when the TiO2 catalyst is
coated on a support, it is expected that the masstransfer limitation would play a significant role in
photocatalytic reactions because of the increased diffusional length for diffusion of contaminants from the bulk
solution to the catalyst surface. Therefore, to determine
Ind. Eng. Chem. Res., Vol. 42, No. 24, 2003 6027
r0 )
[ ][ ]
dCb
VL
) koCb )
VR
dt
km,ext(Cb - Cs) )
krKCs
(3)
1 + KCs
(4)
Cs )
km,ext
C
km,ext + k b
(5)
ro ) koCb )
krkm,ext
1
C )
Cb (6)
km,ext + kr b
1
1
+
kr km,ext
1
1
1
1
1
)
+
)
+
ko kr km,ext krK km,ext
(7)
1
1
1
1
+
+
)
ko kr km,int km,ext
(8)
To determine intrinsic kinetic parameters, it is necessary to find out the mass-transfer rates, so that true
kinetic parameters could be deduced from the overall
observed rates.
Effect of Internal Mass Transfer. The influence
of the internal mass transfer on the observed photocatalytic reaction rate can be determined by the magnitude of the Thiele modulus. The thin catalyst film can
be considered a porous slab, and for the first-order
reaction, the Thiele modulus (H) is given by
H ) H
kr
De
(9)
6028 Ind. Eng. Chem. Res., Vol. 42, No. 24, 2003
Figure 11. Measurement of the mass-transfer coefficient, km, as a function of the Reynolds number. Experimental conditions: VL ) 2.4
10-4 m3, T ) 303 K, A ) 1.96 10-3 m2.
Figure 12. Photocatalytic degradation of Eosin B at low initial concentration. Experimental conditions: SC illumination, Q ) 5.2
10-6 m3/s, I ) 33 W/m2, w ) 5.2 10-3 kg/m2, VL ) 2.4 10-4 m3, T ) 303 K, pO2 ) 60.8 kPa, natural pH.
VL
dCb
) -km,extA(Cb - Cs)
dt
(10)
Ind. Eng. Chem. Res., Vol. 42, No. 24, 2003 6029
(11)
kr )
ksawnI
1 + awnI
(12)
6030 Ind. Eng. Chem. Res., Vol. 42, No. 24, 2003
Figure 14. Effect of the light intensity and catalyst layer thickness on the photocatalytic degradation of Eosin B. Experimental
conditions: SC illumination, C0 ) 16 mmol/m3, Re ) 141, VL ) 2.4 10-4 m3, T ) 303 K, pO2 ) 60.8 kPa, pH0 ) 5, natural pH.
kp
KO2pO2
1 + KO2pO2
(13)
When the data were fitted with the above equation, the
value of KO2 obtained was 0.478 kPa-1.
Effect of Temperature. The photocatalysis reaction
is usually not very temperature-sensitive because the
band-gap energy (3.2 eV for TiO2) is too high to be
overcome by thermal activation energy (kT ) 0.026 eV
at room temperature). For example, the overall activation energy for photocatalytic degradation of 4-chlorophenol has been reported as 16 kJ/mol,1 while for
methylene blue, it is 60.6 kJ/mol.34 Increasing the
reaction temperature may increase the oxidation rate
of organic compounds at the interface, but it also
reduces the adsorptive capacities associated with the
organics and dissolved oxygen. Figure 16 shows the
effect of temperature on the photocatalytic degradation
of Eosin B. Once again, after correction for mass
transfer using km values, true kinetic rate constants are
obtained from the observed rate ko (given by the slope
of the lines in Figure 15). The activation energy was
determined from the slope of the Arrhenius plot (see
Figure 16) as 25.7 kJ/mol.
Effect of the pH of the Solution. In all of the
previous experimental results, the initial pH of the
solution was 5, and the subsequent reactions were
allowed to continue at natural pH. Some studies have
been conducted to investigate the effect of pH on the
Ind. Eng. Chem. Res., Vol. 42, No. 24, 2003 6031
Figure 15. Effect of the partial pressure of oxygen on the photocatalytic degradation of Eosin B. Experimental conditions: SC illumination,
C0 ) 16 mmol/m3, Re ) 141, VL ) 2.4 10-4 m3, I ) 33 W/m2, w ) 5.2 10-3 kg/m2, T ) 303 K, pH0 ) 5, natural pH.
Figure 16. Effect of the temperature on the photocatalytic degradation of Eosin B. Experimental conditions: SC illumination, C0 ) 16
mmol/m3, Re ) 141, VL ) 2.4 10-4 m3, I ) 33 W/m2, w ) 5.2 10-3 kg/m2, pO2 ) 60.8 kPa, pH0 ) 5, natural pH.
6032 Ind. Eng. Chem. Res., Vol. 42, No. 24, 2003
Figure 17. Effect of the pH on the photocatalytic degradation of Eosin B. Experimental conditions: SC illumination, C0 ) 16 mmol/m3,
Re ) 141, VL ) 2.4 10-4 m3, I ) 33 W/m2, w ) 5.2 10-3 kg/m2, T ) 303 K, pO2 ) 60.8 kPa.
TiOH T TiO- + H+
(14)
where
4.3ksxwI0.83
1 + 4.3xwI0.83
Conclusions
A swirl-flow monolithic-type reactor was used to
evaluate the intrinsic kinetic parameters for photocatalytic degradation of a dye, Eosin B when the TiO2
catalyst was immobilized on the Pyrex glass substrate
by a dip-coating technique. The reactor is unique for the
kinetic study of photocatalysis because it can be used
to measure, apart from various rate constants, the
effects of the catalyst layer thickness and light intensity
on the rate constants when light falls directly on the
catalyst (SC illumination) or when it has to travel
through absorbing and scattering liquid media (LC
illumination). It was found that external mass-transfer
resistance exists and, therefore, true kinetic rates were
calculated from the observed reaction rate after correcting for mass resistance. Experiments were also conducted to investigate the effect of temperature, oxygen
concentration, and pH. The photocatalytic rates reported
with the Degussa P25 catalyst can be described by the
following equation:
r ) km(Cb - Cs) )
kr(I,w) KCs
1 + KCs
Ind. Eng. Chem. Res., Vol. 42, No. 24, 2003 6033
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