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In this study, the role of mixing hydrodynamics during the solgel synthesis of titania nanoparticles and the consequences on their photocatalytic properties were investigated. For the rst time three different T-mixer geometries
were tested. Alcoholic solutions of titanium tetra-isopropoxide and water were mixed in three different T-mixers
with turbulence promoters and thus different mixing characteristics. The changes of nanoparticle sizes during the
induction time of the solgel process were followed by dynamic light scattering and velocity and turbulence elds
were simulated by Computational Fluid Dynamics (CFD) for the three T-mixer geometries. The results indicated that
macro-mixing is crucial during the rst step as it determines the nucleation rate and then the primary particle size.
The micro-mixing has an inuence on particle properties, especially on particle stability. Titanium dioxide nanoparticles synthesized by the solgel process were deposited on alumina supports. A homogeneous lm of about 200 nm
was deposited in all cases. Degradation of Acid Orange 7 (AO7) was used to evaluate the photocatalytic activity of
TiO2 coatings. No difference was observed between the photoactivity of synthesized TiO2 . Total mineralization of the
dye occurred after 24 h irradiation.
2013 The Institution of Chemical Engineers. Published by Elsevier B.V. All rights reserved.
Keywords: Water treatment; Titanium dioxide; Solgel synthesis; Photocatalysis; Mixing
1.
Introduction
2390
(1)
(2a)
(2b)
Krysa,
2011; Velegraki et al., 2006). So, the aim of this study
is not to establish the degradation pathways and the formation of by-products which have already been fully described
(Vinodgopal et al., 1996; Bauer et al., 2001; Stylidi et al., 2003).
The novelty of this paper lies within the two following
aspects: rst, the effects on particle size evolution of several mixing-reactor geometries with the same inlet ow rates
were compared. Indeed, to our knowledge, most of the studies
investigated the effect of the inlet ow rates on the particle distribution size in the same reactor geometry. Second,
the consequences of the mixing conditions employed during
solgel synthesis on subsequent photocatalytic properties of
TiO2 coatings were investigated. The originality of this work
is to focus on the role of uid dynamics on both particle
size/stability of the sol (local scale) and photocatalytic performance (pilot scale).
In this present work, particle characterization and photocatalysis process performances were investigated from an
experimental point of view and ow behavior in the T-mixer
was characterized using Computational Fluid Dynamics (CFD).
2.
2.1.
Solgel reactions
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2.2.
Dip-coating reactor
2.3.
Characterization
2392
3.
Governing equations and numerical
details
2.4.
Photocatalytic reactor
Photocatalysis properties of the synthetized TiO2 coating were investigated by following the degradation of
Acid Orange 7 (AO7) as a model pollutant (Fig. 3). AO7
(purity > 85%) was purchased from Aldrich and used without further purication. The photocatalytic reactor consists
in a batch glass reactor composed of two tanks separated
by a UV transparent Plexiglas wall (Fig. 4). The rst one
(height = 200 mm, width = 50 mm, depth = 110 mm) contains a
UV light ( = 365 nm, Philips pL-L 24W/10/4P) and the second
one (height = 200 mm, width = 85 mm, depth = 110 mm) contains contaminated water, an alumina support with TiO2
coating and an air diffuser. The irradiance after the plexiglass
wall was about 22.76 W/m2 . The dissolved oxygen reached
a value of 8 mg O2 /L and only a slight decrease of the dissolved O2 (10%) was observed after 16 h of irradiation. The
AO7 degradation under UV irradiation was monitored using
a UVvis spectrophotometer (UV-2401 PC Shimadzu). The
concentration of the model pollutant is calculated by the
calibration curve obtained from the absorbance of solutions
(max = 485 nm) at different concentrations. The photocatalytic
activity of the TiO2 coatings elaborated in the three solgel
reactors was determined by studying the AO7 degradation
under UV irradiation. Firstly, alumina supports with or without TiO2 coating were placed in a 10 mg/L solution of AO7
under dark conditions for 30 min with bubbling air in order to
reach adsorption equilibrium. Then the UV-lamp was turned
on and at scheduled times, 1 mL of sample was taken from
the reactor. The pH was the natural pH of the dye (7.2) and
(3)
C k2
Sct
(4)
where C is a numerical constant equal to 0.09, Sct is the turbulent Schmidt number equal to 0.7, k is the turbulence kinetic
energy and the turbulence energy dissipation rate which is
computed from the CFD turbulence model.
Mixing at the micro-scale was characterized by estimating the spacial distribution of the local Reynolds number, Rel ,
which uses the local turbulence level and is given by:
Rel =
(5)
(v)
4.
4.1.
In Fig. 5, the mean particle size prepared under the same operating conditions in the three T-mixers is reported, versus time.
It can be seen that the mean particle size stabilizes between
2393
4.2.
Fig. 6 Change of the TiO2 nanoparticle size distribution during the induction period of the solgel process using Ts , Tb and
Tn .
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Fig. 7 SEM micrographies of the alumina support with and without TiO2 coating. Top view without TiO2 coating (a), top
view with TiO2 coating (b) and front view with TiO2 coating (c).
coatings were observed using SEM (Fig. 7) in order to examine
their morphology and defects.
With all the samples obtained, similar TiO2 coatings with a
homogeneous thickness of about 200 nm were observed. TiO2
completely enveloped grains composing the alumina support
(Fig. 7c). However, cracks appeared on the lm surface. This
phenomenon was also noticed by Tian et al. and is attributed
to the removal of residual hydroxyl and organic groups during the heating process (Tian et al., 2009). No difference was
observed between coating morphology obtained from sols
synthesized in the three T-mixers.
4.3.
amount of TiO2 coated ranged from 4.4 to 6.6 mg. Such a small
difference in the mass of TiO2 could explain the very similar
observed kinetics. So the preparation of TiO2 nanoparticles
with three different T-mixers gives particles which present
the same photocatalytic activity. The evolution of the AO7
UVvisible spectrum during irradiation is shown in Fig. 9.
It appears that the visible chromophor ( = 485 nm) strongly
decreases and corresponds to the breakdown of the N N bond
or C N bond as mentioned by Konstantinou and Albanis
(2004) and Zhang et al. (1998). During the rst step of AO7
oxidation by photocatalysis, the main organic by-products
identied were benzene sulphonic acid, sulphoanilic acid,
1,4-naphthoquinone, phtalic acid (Vinodgopal et al., 1996) quinine and 4-hydroxybenzene sulphonic acid (Bauer et al., 2001;
Stylidi et al., 2003). The last organic by-products before complete mineralization were aliphatic acids. Since the majority
of the by-products contain a naphthalene group or a benzene
ring, which both strongly adsorb light at = 254 nm, it is consistent to monitor the variation of the absorbance at = 254 nm
(A254nm ) versus time. Indeed, the decrease of A254nm indicates
the opening of the rings. Then, as suggested by Shinde et al.
(2009), a simplication could be made by correlating the rate
of decrease of A254nm to the rate of mineralization:
d(TOC)
d(A254nm )
dt
dt
(7)
4.4.
Hydrodynamics in T-mixers
Fig. 5 shows that sol synthesized with Tb has a different behavior than sol synthesized with Ts and Tn . The only difference
between the three experiments stands in the mixer geometry
and could therefore be explained by differences in hydrodynamics and characteristic times in the mixer.
The detailed mechanisms of mixing are difcult to observe
experimentally due both to spatial limitations and to the very
short time scales involved. At this point, CFD can be used to
investigate the characteristics of mixing in the chemical reactors. Although a direct validation through comparison with
experimental data would be preferred, it has been proved that
CFD is a reliable tool that can be trusted in order to evaluate
trends and orders of magnitude for quantities such as ow
eld and concentration gradient in such geometries (Marchisio
et al., 2006; Liu and Fox, 2005; Bothe et al., 2006).
Under perfect mixing conditions, the output local relative concentration would be c0 /2 =0.5. Concentration gradients
in a (x, y) plane at a z position can then be represented by
I = (x,y) (c(x, y) (c0 /2))2 . Simulation results enable concentration gradients to be plotted versus the z-axis (vertical pipe)
as shown in Fig. 11. I is an image of macro-scale segregation,
the smaller it is, the better mixing is. For all geometries, concentration gradients appear at the inlet and then disappear
progressively by convection and turbulent mixing along the
z-axis. It rapidly reaches a very low level and macro-scale segregation disappears in the rst section from z = 0 to z = 20 mm
along the z-axis and the uid leaving the reactors is completely
mixed. This rapid mixing is mainly due to the vortex initiated
by eccentric arms (Fig. 12). The relative concentration in the
(x, y) plane sections along the z-axis is shown for the three
T-mixers in Fig. 13. As can be seen, from z = 30 mm, mixing
is completed and there is no longer any concentration gradient and segregation. Before z = 20 mm, c ranges from 0.3
to 0.7. Macro-mixing characteristics in the T-mixers seems
comparable.
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2396
2397
Fig. 14 , k and Rel in the three T-mixers in the reaction region from z = 2 mm (bottom) to z = 18 mm (top).
Thus, the present results suggest that small-scale convection after nucleation, meaning micro-mixing, could have an
effect on particle stability and mean size. Indeed, particles
synthesized in the higher turbulence mixer are larger, less stable and tend to agglomerate more rapidly. Marchisio et al. have
investigated the effect of hydrodynamics on particle stability
with time with a quite similar vortex reactor. They showed for
a high Da number, the initial particle size is larger and particles tend to aggregate rapidly whereas when Da decreases,
initial size is smaller and particles are more stable over time
(Marchisio et al., 2009). In their case, increasing the inlet velocity leads to higher macro-mixing at the mixer entrance. Then
the nucleation of very ne and numerous particles, which
are more stable, occurs. With their geometry, the inuence of
turbulence after nucleation could not be tested. On the contrary, the present study enables the conrmation of the effect
of shear-induced diffusion. These experimental results underline the importance of a well-tailored mixer which is not easy
to produce, as reaction time-scales are not well-known.
Differences observed in Tb compared with Tn and Ts
suggest that nucleation occurred around the rst bafe (at
z = 11 mm) and then growth proceeded after this bafe (for the
current inlet velocity). Then, knowledge of residence time in
this region would enable the typical particle formation time
to be estimated.
The particle tracing function of Comsol software was used
in order to evaluate the residence time in the reaction region.
Here, particle tracing is used as a tool to simply estimate an
2398
tz = 2 (ms)
(ms)
tz = 11 (ms)
(ms)
tz = 20 (ms)
(ms)
tz = 200 (ms)
(ms)
Ts
Tb
Tn
5.9
1.3
11.0
1.9
15.7
2.2
113.3
0.7
5.9
1.0
11.0
2.5
13.6
2.8
99.8
11.0
5.9
1.1
10.1
1.9
15.4
1.8
37.1
4.4
literature. Table 2 summarizes the characteristic particle formation time-scale found in the literature for solgel synthesis.
The value of this typical time is very dependent on operating
conditions. The order of magnitude found in this study seems
consistent with values available in the literature. Nonetheless,
it can be noted that the characteristic time found in this study
is not in accordance with the rst hydrolysis time of about several tens of milliseconds given by Rivallin et al. (2005) in similar
operating conditions. Based on this latter value, the reaction
zone, and thus the particle formation area, was expected after
z = 40 mm, which justied the initial bafe and narrow pipe
location.
These results conrm the rapidness of the solgel reaction
which is limited by the mixing rate. Adequate mixers which
can achieve an efcient mixing within a few milliseconds must
be found. T-mixers like the one presented could be optimized
for the velocity range tested. Other static mixers must be considered with well-located turbulence promoters. CFD can be
a reliable tool in order to calibrate appropriate mixers for a
specic nanoparticle precipitation application.
Precipitation is a complex phenomenon; the particle eld
and its evolution reect spatial variations of convection, diffusion and chemical reaction. It is well-known that solgel
synthesis is based on the hydrolysis and polycondensation of
metal compound precursors and that these two types of reactions occur simultaneously in a conventional solgel method,
i.e. polycondensation begins before complete hydrolyzation of
the metal compound. This leads to a complicated state around
the metal ion which depends on the synthesis parameters.
The way those parameters affect the process is still not clear.
Rare studies about the mixing effect during particle synthesis
have all underlined the importance of controlling mixing in
order to get the desired particle size distribution. The present
study proves that the mixing quality might have an effect not
only on particle size but also on their stability.
Table 2 Estimation of typical particle formation time under various operating conditions.
Reference
Typical particle
formation time
(ms)
1.05
7.7
1.7
3.2
30
59
6
Operating conditions
5.
Conclusion
2399
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