Journal of Chemical Engineering of Japan, Vol. 49, No. 2, pp.

130–135, 2016 Research Paper

Process Intensification of Photocatalytic p-Anisaldehyde

Synthesis by Using Mini Batch Reactor and UV-LED
Dalia Heggo1, Haitham Mohamed1, Shinichi Ookawara1,2 and
Yoshihisa Matsushita1
1
Department of Chemical and Petrochemical Engineering,
Egypt-Japan University of Science and Technology, P.O. Box 179, New Borg El-Arab postal code 21934,
Alexandria, Egypt
2
Department of Chemical Engineering, Graduate School of Science and Technology,
Tokyo Institute of Technology, 2-12-1 O-okayama, Meguro-ku, Tokyo 152-8552, Japan

Keywords: Process Intensification, Photocatalysis, UV-LED, Mini Reactor

The process intensification of photocatalytic p-anisaldehyde (p-MB) synthesis was examined by relying on a mini glass
reactor and UV-LED lamp. TiO2 photocatalyst was highly loaded in ethyl acetate solvent and dispersed by a magnetic stir-
rer and oxygen bubbling in a glass cell reactor. The reactor was irradiated by the UV-LED lamp in the UV intensity range
less than 224 mW/cm2 at the reactor surface. The generation rate of p-MB (GR) from p-methoxytoluene (p-MT) was evalu-
ated by GCMS. The GRs per lamp power attained in this study were found to be much higher than those in the previous
studies on the photocatalytic p-MB synthesis from p-MT or even from p-methoxy alcohol. The attained high reaction ef-
ficiency can be attributed to the high efficiency of the UV-LED and small size of the reactor that enabled better penetra-
tion of UV light through the entire volume of the reactor in spite of high catalyst loading.

As an alternative to the above routes, p-anisaldehyde can

Introduction
p-Anisaldehyde (4-Methoxybenzaldehyde) is one of the
intermediates in pharmaceutical and perfumery industries.
Synthetic routes to p-anisaldehyde usually involve oxida-
tion of p-methoxytoluene in the presence of catalyst at high
temperatures (Bentrup et al., 2003). Generally speaking, in
the liquid phase, substituted benzaldehydes are synthesized
from the corresponding toluene in the presence of Co, Ce
and Mn salts in acetic acid medium or by electrochemical
methods (Tzedakis and Savall, 1992). However, byproducts
from those processes have been an environmental issue
(Shimizu et al., 1989; Ueshima and Saito, 1992; Reddy et
al., 1997, 1999). In the vapor phase, p-anisaldehyde is also
synthesized from p-methoxytoluene by catalytic oxidation
over V2O5/CaO–MgO (Reddy et al., 1999), Cs-V/TiO2 or
Cs-VSb/Al2O3 with alkali metals at high temperatures (Yoon
et al., 2007). However, the selective production of aro-
matic aldehydes was much more complicated in the vapor
phase, because of the high tendency of aldehydes to be con-
secutively oxidized very fast to acids and deeper oxidized
products (Bentrup et al., 2000). As an environmentally be-
nign process, on the other hand, hypervalent iodine medi-
ated oxidation was examined for the synthesis of p-MB with
PhI(OAc)2/NaY or PhI(OAc)2/Al2O3, although this process
requires microwave irradiation (Reddy et al., 1999; Alvarez
et al., 2006)
Received on March 18, 2015; accepted on May 9, 2015
DOI: 10.1252/jcej.15we042
Correspondence concerning this article should be addressed to D.
Heggo (E-mail address: Che.dalia@gmail.com).
be synthesized by photocatalytic oxidation with TiO2 from
p-methoxytoluene (Bouquet-Somrani et al., 1995) or often
from p-methoxybenzyl alcohol (Farhadi et al., 2005; Ad-
damo et al., 2008b; Yurdakal et al., 2008, 2009, 2012). It is
noted that p-methoxybenzyl alcohol can be derived from
p-methoxytoluene.
Recently, the photocatalytic processes have received atten-
tion mainly in the field of water and wastewater treatment
due to its ability to completely oxidize many organic pol-
lutant and in the liquid phase (Ramos et al., 2014a, 2014b,
2014c; Gar Alalm et al., 2016) as well as in the gaseous phase
(Fu et al., 1995; Luo and Ollis, 1996; Augugliaro et al., 1999)
at low cost. However, handling such as transportation and
recovery of nanoparticles dispersed in the liquid phase as
well as its low reaction rate has prevented making the photo-
catalytic processes widespread.
Photocatalytic microreactors, of which the inner wall is
covered with a thin film of photocatalyst, can be expected
to enhance the reaction rate and to eliminate the necessity
of transportation and recovery operations of nanoparticles
(Addamo et al., 2008a). Actually, the microreactors have
been successfully examined in the applications to photoreac-
tions (Fukuyama et al., 2004; Gorges et al., 2004; Nakamura
et al., 2004; Yamashita et al., 2004; Jähnisch and Dingerdis-
sen, 2005; Maeda et al., 2005; Takei et al., 2005; Teekateer-
awej et al., 2005) by taking advantage of the features unique
to microspace such as short molecular diffusion distance
and fast mixing, extremely effective heat exchange, laminar
flow, and large surface-to-volume ratio (Ehrfeld et al., 2000;
Aoki et al., 2004; Yoshida et al., 2005).
Recently, it was reported that p-anisaldehyde could be

130  Copyright © 2016  Journal

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of Chemical
of Chemical
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Engineers,
of Japan
synthesized from p-methoxytoluene with high yield and
high selectivity by employing UV-LED lamps and glass mi-
croreactors, of which the inner surface was coated with TiO2
photocatalyst (Shimoda et al., 2012). However, the feasibility
of industrial application of their findings was unclear due
to the extremely small throughput of the continuous flow
microreactor.
In this study, therefore, the feasibility of process intensi-
fication of this reaction was examined by relying on a small
glass batch reactor, in which the mixture of reactant, solvent
and dispersed TiO2 powder was UV-irradiated with oxygen
bubbling.
We report that the high productivity and high selectivity
of p-anisaldehyde (p-MB) can be achieved even by employ-
ing a batch reactor, and further, both the generation rates
of p-MB (GR) per consumed power and GR per power per
reactor volume are much higher than the GRs found in the
literature. It should be noted that this reaction can be in-
tensified by employing conventional TiO2 catalyst without
the need of high temperature or any toxic oxidizer/costly
synthesized catalysts.
1. Experimental
1.1 Preparation of reactant solution
p-Methoxytoluene (starting substrate) and ethyl acetate
(solvent) were purchased from Sigma-Aldrich, Germany
and were used without further purification. Photocatalyst
powder of titanium dioxide, P25 was purchased from Acros
Organics, USA. The specific surface area of P25 was 51 m2/g,
which was analyzed by BET (BelsorbminiII, BEl Japan Inc.,
Japan). In all of the experiments, 2 wt% of reactant solution
was prepared from 86 µL of p-methoxytoluene (p-MT) and
3.9 mL of ethyl acetate. Further, 0.02 g of P25 powder was
added to the reactant solution so that the catalyst concentra-
tion became 5 g-catalyst/L-mixture.
1.2 Experimental setup and procedures
A quartz cell with the dimensions of 1 cm×1 cm×4.5 cm
(height) was employed as a small-scale batch reactor, which
assures efficient penetration of UV light through the whole
reactor volume due to the UV transparency of quartz and
its small dimensions. The cell has a neck with the length of
9.5 cm.
Figure 1 shows a schematic diagram of the experimental
setup. The reactant mixture was first stirred in the batch cell
at 500 rpm using a magnetic stirrer for 4 h to ensure reach-
ing adsorption equilibrium. Immediately after this step, oxy-
gen gas was continuously fed into the mixture from the
bottom of the cell through 1/16″ polymeric tubing at the ad-
justed flow rates using a micro-plunger pump (CP-DSM-GF,
VICI ValcoInstruments). Before feeding oxygen gas into the
cell, oxygen gas from a gas cylinder was stored in an upside-
down graduated cylinder, of which the inner space was iso-
lated by water in a beaker. The gas flow rates were adjusted
in the range less than 8.7 mL/min at ambient conditions.
Simultaneously, the batch cell was UV-irradiated
Vol. 49  No. 2  2016
Fig. 1 Schematic diagram of experimental setup
1: oxygen cylinder, 2: beaker (to confine oxygen beyond water), 3:
graduated cylinder, 4: micro-plunger pump, 5: Stirrer, 6: glass cell reac-
tor, 7: UV-LED lamp, 8: DC power supply, 9: temperature controller, 10:
chiller
Fig. 2 Successive photocatalytic oxidation of p-methoxytoluene
using a UV-LED lamp with the peak emission of 365 nm
(NLBU21P02, Nichia Corporation). The batch cell was
placed at the horizontal distance of 1 cm from the lamp so
that the cell surface normally faces the lamp. The UV-LED
lamp was cooled by circulating water from a chiller. The UV
intensity was adjusted in the range less than 228 mW/cm2,
by applying a voltage to the LED by using a DC power sup-
ply. The current was monitored by the DC power supply and
the power consumed at the lamp was estimated from the
applied voltage and the resultant current. All of the experi-
ments were carried out at ambient temperature and pressure
conditions.
During irradiation for 4 h, a small amount of sample was
collected from the reactant mixture every hour. The samples
were analyzed by GCMS (GCMS-QPultra2010, Shimadzu
Corp.).
2. Results and Discussion
2.1 Reaction scheme and detected products
In this study, the detected products from p-MT were p-
Malc, p-MB, and p-anisic acid (p-MA). Those products are
considered to be generated successively as shown in Figure
2. Following this scheme, the target material of p-MB is ob-
tained as an intermediate in the successive oxidation from
p-MT.
Figure 3 shows a typical concentration change of p-MT,
p-Malc, p-MB, and p-MA with irradiation time, which was
obtained at an oxygen flow rate=5.9 mL/min and UV inten-
sity=228 mW/cm2. Although it is expected that p-MA can
be further oxidized to CO2 as mentioned in the literature
131

Fig. 3 Concentration change of p-MT, p-Malc, p-MB, and p-MA with
irradiation time (Oxygen flow rate=5.9 mL/min, UV inten-
sity=228 mW/cm2)
(Bouquet-Somrani et al., 1995), it was not taken into ac-
count in this study for focusing on the generation rate of
p-MB from the practical viewpoint.
As can be seen in this figure, the concentration of p-Malc
was small and nearly constant regardless of the sampling
time. The low concentration of p-Malc was consistent regard-
less of operating conditions. p-MB was a major product in
the first hour of UV irradiation. After the elapsed time of
1 h, the concentration of p-MA increases with time. At the
elapsed time of 3 h, the concentration of p-MB reached the
maximum, and subsequently decreased while the concentra-
tion of p-MA kept increasing with time. Taking into account
a previous study on the photocatalytic synthesis of p-MB
from p-Malc (Yurdakal et al., 2008, 2009, 2012; Addamo et
al., 2008b), the concentration change of each product also
validates the reaction scheme in Figure 2. The constant
low concentration of p-Malc may imply that it can be eas-
ily oxidized, viz., immediately oxidized once generated. On
the other hand, Figure 3 shows that subsequent oxidization
of p-MB causes the lower selectivity thereof, although this
step does not appear to be fast. Therefore, it is necessary to
choose an appropriate irradiation period for achieving both
high yield and high selectivity.
2.2 Effect of operating conditions
To examine the effect of operating conditions, such as
the UV light intensity and the flow rate of oxygen, the gen-
eration rate of p-MB (GR) [mmol/h] and its selectivity were
calculated from the concentration of p-MB and the afore-
mentioned coexisting products just after 1 h of irradiation.
Here, the GR is calculated assuming the solution volume is
constant in spite of sampling and evaporation. As shown in
Figure 4, the GR increased with the UV light intensity at a
fixed oxygen flow rate of 8.7 mL/min, while p-MB was not
generated without UV irradiation. In the blank experiment
without catalyst loading (oxygen flow rate=5.9 mL/min, UV
intensity=228 mW/cm2), the generation rate of p-MB was
extremely small at 0.005 mmol/h. Therefore, this reaction
can be reasonably regarded as photocatalytic.
On the other hand, the selectivity is nearly constant, al-
though it slightly dropped only at the highest UV intensity
132
Fig. 4 Effect of UV light intensity on generation rate and selec-
tivity of p-MB at the irradiation time of 1 h (oxygen flow-
rate=8.7 mL/min)
Fig. 5 Effect of oxygen flow rate on generation rate and selectiv-
ity of p-MB at the irradiation time of 1 h (UV light inten-
sity=228 mW/cm2)
in this work. The constant selectivity implies that the gener-
ation rate ratio of p-MB and p-MA is nearly constant in the
examined UV-intensity range, while both of the generation
rates increased with UV intensity.
In Figure 5, at a fixed UV intensity of 228 mW/cm2, the
GR rapidly increased in the oxygen flow rate range less than
2.9 mL/min, and it nearly became constant in the higher
range. Without oxygen bubbling, the GR was significantly
small. The results imply that oxygen gas is a source of oxi-
dant in this reaction. The constant GR in the higher range of
oxygen flow rates was probably caused by the constant oxy-
gen concentration in the liquid phase, i.e. a saturation con-
centration. Regarding the selectivity, it was nearly constant
in the examined flow rate range. The results imply that the
generation rate ratio of p-MB and p-MA were not affected
by oxygen flow rates in this range.
The reproducibility was examined at some operational
conditions and it was ±7% from the average as can be seen
in Figures 4 and 5. For the evaluation of productivity, the
lower value was taken for the safety of comparison in Table
1.
2.3 Productivity of reaction system
Applicability of photocatalyst to a reaction of interest is
usually examined in terms of conversion, yield, and selectiv-
ity. From the viewpoint of production, however, the reac-
Journal of Chemical Engineering of Japan
 Table 1 Comparison between highest selectivity achieved among this study and literature studies

Irradiation Conversion Selectivity GRp GRpv GRpvm

Type of reaction References
time [h] [%] [%] [µmol/(W·h)] [mmol/(W·h·m3)] [mmol/(W·h·m3 ·gcatalyst)]

Photocatalytic Present studya 3 58 72 2.6 650 130

oxidation of Bouquet-Somrani et al. (1995)b 48 75 60 0.20b 0.56b 1.867
p-MT
Photocatalytic Addamo et al. (2008b)c 4.3 50 56 0.065 0.13 0.20
oxidation of Farhadi et al. (2005)d 1 N/A N/A 2.3 92 368
p-Malc Augugliaro et al. (2009)e 8.8 50 62 1.41 2.82 14.09
Yurdakal et al. (2008)f 2.36 50 60 0.48 0.97 4.83
Yurdakal et al. (2009)g 2.6 50 72 0.55 1.11 3.69
Yurdakal et al. (2012) Solar light simulator 1.5 30 71.5 0.0086 0.057 0.64
(1,500 W)h
Visible light (100 W)i 1.8 10 83 0.042 0.28 3.07
Near UV (125 W)j 0.35 30 66 0.41 2.72 30.17
a
UV intensity=228 mW/cm2; oxygen flow rate=5.9 mL/min; power for UV-LED lamp=32 W.
b
Values mentioned in the table were calculated from the study; solvent volume (acetonitrile) was 360 mL; total power of mercury lamps=500 W. Amount of catalyst
(TiO2)=300 mg.
c
Values mentioned are based on the best selectivity; volume of aqueous suspension=1.6 L; total power (Hg Lamps)=500 W; amount of catalyst (Brookite)=0.64 g.
d
Solvent (acetonitrile) volume=25 mL; mercury lamp power=400 W; amount of catalyst (H3PW12O40/SiO2)=0.25 g; yield% (p-anisaldehyde)=92.
e
Volume of aqueous solution of reactants=0.5 L; power of medium pressure Hg lamp=125 W; amount of catalyst (home-prepared Rutile)=0.2 g; temperature of sus-
pension=300 K.
f
Solvent volume (organic free suspension)=0.5 L; amount of catalyst (HP333)=0.2 g; power of lamp (Hg medium pressure)=125 W.
g
Solvent volume (organic free suspension)=0.5 L; amount of catalyst (HP/50)=0.3 g; power of lamp (Hg medium pressure)=125 W.
h
Solvent volume (water)=150 mL, power of solar box (86 mW/cm2, 450–950 nm)=1,500 W, amount of catalyst (N-HP5-NH4Cl, 128 m2/g)=0.09 g.
i
Solvent volume (water)=150 mL, power of lamp (halogen display lamp, 200 mW/cm2, 450–950 nm)=100 W; amount of catalyst (N-HP2-NH4Cl, 132 m2/g)=0.09 g.
j
Solvent volume (water)=150 mL, power of lamp (medium pressure Hg lamp, 12.20 mW/cm2, 315–400 nm; 100 mW/cm2, 450–950 nm)=150 W; amount of catalyst (N-
HP2-NH4Cl, 132 m2/g)=0.09 g.

tion rate is more important. It is known that the rate of a
photocatalytic reaction in the liquid phase is greatly affected
by the initial concentration of reactant, catalyst loading, and
irradiation energy. Therefore, to compare the productivity of
the reaction system in this study with that of similar works,
three indices related to the generation rate of p-MB (GR)
are defined in this study: GR per power consumed at lamp,
GRp [µmol/(h·W)]; GR per power per reactor volume, GRpv
[mmol/(h·W·m3)]; and GR per power per volume per mass
of catalyst, GRpvm [mmol/(h·W·m3 ·gcatalyst)].
In the literature, high-power Hg lamps were often used
for irradiating the reaction systems with UV light. The cost
of UV lamps is apparently one of the drawbacks that hinder
the applications of photocatalysis in industry. LED lamps,
which are becoming popularity nowadays, are regarded
as energy-efficient and long-life devices for emitting light.
Therefore, a UV-LED lamp was employed in this study to
intensify the photocatalysis. To evaluate the systems based
on energy efficiency, the GR is divided by the lamp power in
all of the GR indices.
The present research is motivated by the expectation that
microreactors or even small reactors could bring about bet-
ter productivity than conventional-size reactors. To evaluate
the effect of reactor size, the GR was divided by reactor vol-
ume in the second and third indices.
On the other hand, it is known that the higher catalyst
loading does not necessarily result in higher reaction rate,
probably because the higher concentration causes higher
turbidity that hinders light penetration through the slurry. It
was shown that the optimum catalyst concentration (TiO2,
P25) was 2 g/L in the examined range of 0.25 to 4 g/L for
the degradation of phenol in a 1-L reactor (Chiou et al.,
2008). For the synthesis of p-MB, larger reactors (0.36–1.6 L)
are operated with lower catalyst concentrations (TiO2,
0.4–0.83 g/L), as can be calculated from the data in Table
1 (Bouquet-Somrani et al., 1995; Addamo et al., 2008b;
Yurdakal et al., 2008, 2009; Augugliaro et al., 2009). This is
another reason why the smaller reactor was employed in this
study. The shorter light pass enables sufficient light penetra-
tion through the whole reactor volume even with the high
turbidity. To evaluate the effect of catalyst concentration, the
GR is divided by the mass of catalyst in the third index.
Before the comparison, it should be noted that the experi-
mental conditions in the previous works as well as in this
study were not necessarily optimized in terms of the defined
indices above. However, it can be reasonably expected that
the previous works reported the best result in their research
as we did here. Actually, the best result shown in Figure 3
was used to calculate the GR indices in this study. When
several results were reported in a previous work, the best
result was selected to calculate the GR indices. Therefore,
the comparison is reasonably fair and useful to validate
our strategy for intensifying the photocatalytic synthesis of
p-MB from p-MT.
Table 1 shows the results of yield, selectivity, and irradia-
tion time, which were reported in this study and in similar
previous works that examined photocatalytic synthesis of
p-MB. By using the reported results, the reaction rates of
p-MB (GR) were calculated. Subsequently, the GRp, GRpv,
and GRpvm were calculated by using the experimental condi-
tions in each work.
As seen in the table, the small reactor with a UV-LED in
this study attained the best productivity of p-MB in terms of
GRp and GRpv among the similar works. Only one previous
work showed better productivity in terms of GRpvm (Farhadi
et al., 2005). The GRpvm achieved in this study could have a

Vol. 49  No. 2  2016 133

somewhat lower value in spite of high GRp and GRpv values regardless of the light source when compared to the present
since the reaction system operated with higher catalyst load- study (Yurdakal et al., 2012).
ing as mentioned above.
In the literature, there is only one work in which p-MB
Conclusion
was synthesized from p-MT by TiO2 photocatalysis (Bou-
quet-Somrani et al., 1995). They reported that conversion, The miniaturization of a batch reactor and the use of
selectivity and irradiation time were 75%, 60% and 48 h, UV-LED enabled photocatalytic synthesis of p-anisaldehyde
while in this work those were 58%, 72% and 3 h, respec- from p-methoxytoluene with high productivity and high
tively. It is worth mentioning that the GRp, GRpv, and GRpvm selectivity, due to the high-efficiency of the UV-LED and
of this study were one order, three orders and two orders of better light penetration through the reactor volume in spite
magnitude greater than those indices in their work. The su- of high catalyst loading. The higher production rate of
periority here in terms of GRpvm is somewhat smaller com- p-MB with lower energy consumption can be achieved by
pared to GRpv due to high catalyst loading. numbering-up the reaction system examined in this study.
In the rest of previous works, the starting material was The optimum extent of miniaturization as well as optimum
p-Malc instead of p-MT. As shown in Figure 2, p-Malc is operating conditions, such as initial concentration, catalyst
generated from p-MT as a first intermediate in successive loading, solvent and higher UV intensity is of further inter-
oxidation. Therefore, the GR indices are expected be greater est for realizing its industrial applications. Therefore, the ap-
in those previous works. However, surprisingly, the present plication of microreactors for this synthesis is still within the
study gave much better values. scope of further research.
A previous work argued that the brookite TiO2 with high
specific surface area (SSA) (82 m2/g) they prepared resulted Acknowledgements
in 3-fold higher selectivity than commercial TiO2. However,
The first and second authors are grateful to the Egyptian ministry of
their GR indices were found to be very low compared to this higher education for providing a PhD scholarship, Egypt-Japan Uni-
study with commercial TiO2 P25 with low SSA (51 m2/g). versity of Science and Technology (EJUST) for supporting them, and
The difference in productivity can be attributed to the ef- Technology Management Department of E-JUST for GCMS analysis.
ficiency of lamp; UV intensity of 228 mW/cm2 is given by
32 W UV-LED in this study, while those are 17.5 mW/cm2 Nomenclature
and 500 W in their work (Addamo et al., 2008b).
GR = generation rate of p-Anisaldehyde [mol/h]
Another study examined the same reaction with
GRp = GR per lamp power [mol/(h·W)]
H3PW12O40/SiO2 catalyst. Their GRp and GRpv indices are
GRpv = GR per lamp power per reactor volume [mol/(h·W·m3)]
lower than those of this study, while their GRpvm took greater GRpvm = GR per lamp power per rector volume per mass of
values (Farhadi et al., 2005). However, conversion and selec- catalyst [mol/(h·W·m3 ·gcatalyst)].
tivity were not mentioned in their study. LED = light emitting diode [—]
On the other hand, a research group applied the rutile p-MT = p-Methoxy toluene [—]
TiO2 they prepared to the same reaction. All of the GR indi- p-MB = p-Anisaldehyde [—]
ces were found to take lower values in spite of the high SSA p-Malc = p-Methoxybenzyl alcohol [—]
(107 m2/g) of their catalyst. They also reported that com- p-MA = p-Anisic acid [—]
mercial TiO2 P25 resulted in a 12-fold faster reaction rate SSA = specific surface area [m2/g]
compared to their catalyst, while the selectivity was 0.08, UV = ultra violet [—]
which is not practical at all, and hence, this result was not
compared in the table (Augugliaro et al., 2009). Literature Cited
Another group prepared rutile TiO2 with SSA of 107 m2/g Addamo, M., V. Augugliaro, A. Paola, E. García-López V. Loddo,
(Yurdakal et al., 2008), and modified it to enhance the selec- G. Marcí and L. Palmisano; “Photocatalytic Thin Films of TiO2
tivity of p-MB with SSA of 118 m2/g (Yurdakal et al., 2009). Formed by a Sol–Gel Process Using Titanium Tetraisopropoxide as
Although the selectivity was improved, the GR indices were the Precursor,” Thin Solid Films, 516, 3802–3807 (2008a)
still small with a UV intensity of 10 mW/cm2, as can be seen Addamo, M., V. Augugliaro, M. Bellardita, A. Di Paola, V. Loddo,
in the table. G. Palmisano, L. Palmisano and S. Yurdakal; “Environmentally
Friendly Photocatalytic Oxidation of Aromatic Alcohol to Alde-
Further, in 2012, the same group prepared N-doped TiO2
hyde in Aqueous Suspension of Brookite TiO2,” Catal. Lett., 126,
catalysts to enhance the rate of the same reaction with vis-
58–62 (2008b)
ible light. They reported the results obtained with three dif- Alvarez, H. M., D. P. Barbosa, A. T. Fricks, D. A. G. Aranda, R. H. Val-
ferent light sources: solar light simulator (1,500 W), visible dés and O. A. C. Antunes; “Production of Piperonal, Vanillin, and
light lamp (100 W), and near UV (125 W) lamps. The GR p-Anisaldehyde via Solventless Supported Iodobenzene Diacetate
indices with the solar light simulator were extremely small Oxidation of Isosafrol, Isoeugenol, and Anethol under Microwave
because 90% of the emitted irradiance from light was cut Irradiation,” Org. Process Res. Dev., 10, 941–943 (2006)
as they mentioned. It probably happened to simulate the Aoki, N., S. Hasebe and K. Mae; “Mixing in Microreactors: Effectiveness
spectrum of solar light. However, their reaction system with of Lamination Segments as a Form of Feed on Product Distribu-
N-doped TiO2 catalyst was found to give smaller GR indices tion for Multiple Reactions,” Chem. Eng. J., 101, 323–331 (2004)

134 Journal of Chemical Engineering of Japan

Augugliaro, V., S. Coluccia, V. Loddo, L. Marchese, G. Martra, L. Palmi-
sano and M. Schiavello; “Photocatalytic Oxidation of Gaseous
Toluene on Anatase TiO2 Catalyst: Mechanistic Aspects and FT-IR
Investigation,” Appl. Catal. B, 20, 15–27 (1999)
Augugliaro, V., V. Loddo, M. J. López-Muñoz, C. Márquez-Álvarez,
G. Palmisano, L. Palmisano and S. Yurdakal; “Home-Prepared
Anatase, Rutile, and Brookite TiO2 for Selective Photocatalytic
Oxidation of 4-Methoxybenzyl Alcohol in Water: Reactivity and
ATR-FTIR Study,” Photochem. Photobiol. Sci., 8, 663–669 (2009)
Bentrup, U., A. Bruckner, A. Martin and B. Lucke; “Selective Oxidation
of p-Substituted Toluenes to the Corresponding Benzaldehydes
over (VO)2 P2O7 : An in Situ FTIR and EPR Study,” J. Mol. Catal.
Chem., 162, 391–399 (2000)
Bentrup, U., A. Martin and G.-U. Wolf; “Thermal Behaviour, Redox
Properties, and Catalytic Performance of Alkali-Promoted V2O5
Catalysts in the Selective Oxidation of p-Methoxytoluene: A Com-
parative Study,” Catal. Today, 78, 229–236 (2003)
Bouquet-Somrani, C., A. Finiels, P. Geneste, P. Graffin, A. Guida, M.
Klavar and J.-L. Olivé; “Photocatalytic Oxidation of Substituted
Toluenes with Irradiated TiO2 Semiconductor. Effect of Zeolite,”
Catal. Lett., 33, 395–400 (1995)
Chiou, C. H., C. Y. Wu and R. S. Juang; “Influence of Operating Pa-
rameters on Photocatalytic Degradation of Phenol in UV/TiO2
Process,” Chem. Eng. J., 139, 322–329 (2008)
Ehrfeld, W., V. Hessel and H. Löwe; Microreactors: New Technology for
Modern Chemistry, pp. 5–12, Wiley-VCH, Weinheim, Germany,
(2000)
Farhadi, S., M. Afshari, M. Maleki and Z. Babazadeh; “Photocatalytic
Oxidation of Primary and Secondary Benzylic Alcohols to Car-
bonyl Compounds Catalyzed by H3PW12O40/SiO2 under an O2
Atmosphere,” Tetrahedron Lett., 46, 8483–8486 (2005)
Fu, X., W. A. Zeltner and M. A. Anderson; “The Gas-Phase Photo-
catalytic Mineralization of Benzene on Porous Titania-Based Cata-
lysts,” Appl. Catal. B, 6, 209–224 (1995)
Fukuyama, T., Y. Hino, N. Kamata and I. Ryu; “Quick Execution of
[2+2] Type Photochemical Cycloaddition Reaction by Continuous
Flow System Using a Glass-Made Microreactor,” Chem. Lett., 33,
1430–1431 (2004)
Gar Alalm, M., A. Tawfik and S. Ookawara; “Solar Photocatalytic Deg-
radation of Phenol by TiO2/AC Prepared by Temperature Impreg-
nation Method,” Desalination Water Treat., 57, 835–844 (2016)
Gorges, R., S. Meyer and G. Kreisel; “Photocatalysis in Microreactors,”
J. Photochem. Photobiol. Chem., 167, 95–99 (2004)
Jähnisch, K. and U. Dingerdissen; “Photochemical Generation and
[4+2]-Cycloaddition of Singlet Oxygen in a Falling-Film Micro
Reactor,” Chem. Eng. Technol., 28, 426–427 (2005)
Luo, Y. and D. Ollis; “Heterogeneous Photocatalytic Oxidation of Tri-
chloroethylene and Toluene Mixtures in Air: Kinetic Promotion
and Inhibition, Time-Dependent Catalyst Activity,” J. Catal., 163,
1–11 (1996)
Maeda, H., H. Mukae and K. Mizuno; “Enhanced Efficiency and Re-
gioselectivity of Intramolecular (2π+2π) Photocycloaddition of
1-Cyanonaphthalene Derivative Using Microreactors,” Chem. Lett.,
34, 66–67 (2005)
Nakamura, H., X. Li, H. Wang, M. Uehara, M. Miyazaki, H. Shimizu
and H. Maeda; “A Simple Method of Self Assembled Nano-Parti-
cles Deposition on the Micro-Capillary Inner Walls and the Reac-
tor Application for Photo-Catalytic and Enzyme Reactions,” Chem.
Eng. J., 101, 261–268 (2004)
Vol. 49  No. 2  2016
Ramos, B., S. Ookawara, Y. Matsushita and S. Yoshikawa; “Photocata-
lytic Decolorization of Methylene Blue in a Glass Channel Micro-
reactor,” J. Chem. Eng. Japan, 47, 788–791 (2014a)
Ramos, B., S. Ookawara, Y. Matsushita and S. Yoshikawa; “Intensication
of Photochemical Wastewater Decolorization Process Using Mi-
croreactors,” J. Chem. Eng. Japan, 47, 136–140 (2014b)
Ramos, B., S. Ookawara, Y. Matsushita and S. Yoshikawa; “Low-Cost
Polymeric Photocatalytic Microreactors: Catalyst Deposition and
Performance for Phenol Degradation,” J. Environ. Chem. Eng., 2,
1487–1494 (2014c)
Reddy, B. M., I. Ganesh and B. Chowdhury; “Vapour-Phase Selective
Oxidation of 4-Methylanisole to Anisaldehyde over V2O5/Ga2O3–
TiO2 Catalyst,” Chem. Lett., 26, 1145–1146 (1997)
Reddy, B. M., M. Vijaya Kumar and K. Jeeva Ratnam; “Selective Oxi-
dation of p-Methoxytoluene to p-Methoxybenzaldehyde over
V2O5/CaO–MgO Catalysts,” Appl. Catal. A, 181, 77–85 (1999)
Shimizu, N., N. Saito and M. Ueshima; “V2O5 Based Catalysts for the
Vapor Phase Oxidation of p-Methoxytoluene to p–Methoxy Benz-
aldehyde,” Stud. Surf. Sci. Catal., 44, 131–138 (1989)
Shimoda, M., S. Ookawara, Y. Matsuhista and S. Yoshikawa; “Charac-
terization of Photo-Microreactor for One-Step Synthesis of An-
isaldehyde from p-Methoxytoluene,” Abstract of 12th Internation-
al Conference on Microreaction Technology, p. 2, Lyon, France
(2012)
Takei, G., T. Kitamori and H. Kim; “Photocatalytic Redox-Combined
Synthesis of -Pipecolinic Acid with a Titania-Modified Microchan-
nel Chip,” Catal. Commun., 6, 357–360 (2005)
Teekateerawej, S., J. Nishino and Y. Nosaka; “Photocatalytic Microreac-
tor Study Using TiO2-Coated Porous Ceramics,” J. Appl. Electro-
chem., 35, 693–697 (2005)
Tzedakis, T. and A. J. Savall; “Ceric Sulfate Oxidation of p-Methoxy-
toluene: Kinetics and Reaction Results,” Ind. Eng. Chem. Res., 31,
2475–2483 (1992)
Ueshima, M. and N. Saito; “Partial Oxidation of p-Substituted Toluenes
to Corresponding Benzaldehydes in Vapor Phase over V2O5–Ti2O
Catalyst,” Chem. Lett., 21, 1341–1344 (1992)
Yamashita, K., Y. Yamaguchi, M. Miyazaki, H. Nakamura, H. Shimizu
and H. Maeda; “Direct Observation of Long-Strand DNA Con-
formational Changing in Microchannel Flow and Microfluidic
Hybridization Assay,” Anal. Biochem., 332, 274–279 (2004)
Yoon, J. W., S. H. Jhung and J.-S. Chang; “Vapor-Phase Oxidation of
Alkylaromatics over V/TiO2 and VSb/Al2O3 Catalysts: Effect of Al-
kali Metals,” Bull. Korean Chem. Soc., 28, 2405–2408 (2007)
Yoshida, J., A. Nagaki, T. Iwasaki and S. Suga; “Enhancement of Chemi-
cal Selectivity by Microreactors,” Chem. Eng. Technol., 28, 259–266
(2005)
Yurdakal, S., G. Palmisano, V. Loddo, O. Alagöz, V. Augugliaro and L.
Palmisano; “Selective Photocatalytic Oxidation of 4-Substituted
Aromatic Alcohols in Water with Rutile TiO2 Prepared at Room
Temperature,” Green Chem., 11, 510–516 (2009)
Yurdakal, S., G. Palmisano, V. Loddo, V. Augugliaro and L. Palmisano;
“Nanostructured Rutile TiO2 for Selective Photocatalytic Oxida-
tion of Aromatic Alcohols to Aldehydes in Water,” Am. Chem. Soc,
130, 1568–1569 (2008)
Yurdakal, S., V. Augugliaro, V. Loddo, G. Palmisano and L. Palmisano;
“Enhancing Selectivity in Photocatalytic Formation of p-Anisal-
dehyde in Aqueous Suspension under Solar Light Irradiation via
TiO2 N-doping,” New J. Chem., 36, 1762–1768 (2012)
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