Journal of Environmental Management 120 (2013) 68e74

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Journal of Environmental Management

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Design and characterization of a multi-phase annular falling-film reactor for

water treatment using advanced oxidation processes
Mohammad Mehrjouei*, Siegfried Müller, Detlev Möller
Working Group for Atmospheric Chemistry and Air Quality, Brandenburg University of Technology (BTU Cottbus), Volmerstrassea 13, D-12489 Berlin, Germany

a r t i c l e i n f o a b s t r a c t

Article history: In this work, a laboratory-scale of a 3-phase [(I) immobilized photocatalyst, (II) polluted water and (III)
Received 16 January 2012 oxygen or ozone] falling-film reactor was designed and developed for heterogenous advanced oxidation
Received in revised form processes. Characterization and assessment of the annular falling film reactor for handling different
27 June 2012
advanced oxidation methods was performed. Degussa P-25 TiO2 particles were immobilized on boro-
Accepted 5 February 2013
silicate glass (BSG) and polymethylmethacrylate (PMMA) tubes and used as a photocatalyst in this study.
Available online 19 March 2013
The characteristics of the falling film reactor, such as the thickness and distribution of falling films and
the level of gas absorption into the liquid falling films, as well as the effect of UVA irradiation on the
Keywords:
Falling film reactor
decomposition of ozone inside the falling film reactor, were studied. The adsorption of a model com-
Advanced oxidation processes pound on the surface of the immobilized catalyst was measured and the photoactivity of the immobi-
AOP lized photocatalyst was evaluated for the degradation of the model compound. Oxalic acid was chosen as
Photocatalysis the model compound in this study.
Water purification Ó 2013 Elsevier Ltd. All rights reserved.
Wastewater treatment

1. Introduction hydroxyl radicals on the molecules of organic and inorganic pol-

Falling film reactors are typically being used for various indus-
trial purposes such as in detergent and surfactant manufacturing.
These industries apply different kinds of falling film reactors in
order to improve the liquidegas interactions during the processes
of sulfonation, chlorination, etc. For example, sulfonation of linier
alkyl benzene (Zaid et al., 2000) and dodecyl benzene (Gonzalez
et al., 1988) has been reported by utilizing falling film reactors.
Based on the application benefits of falling film reactors, an
increasing interest in the use of this form of reactors in water and
wastewater treatments and especially in dealing with advanced
oxidation technologies has been clearly observed in recent years
(Bekbölet et al., 1996; Dojcinovic et al., 2011; Stephan et al., 2011).
Photocatalytic oxidation is one of the advanced oxidation technol-
ogies employed for degradation of organic compounds in water. In
this process, the surface of a semiconductor (photocatalyst) is irra-
diated by appropriate wavelengths in order to generate electrone
hole pairs thereon. The nucleophiliceelectrophilic reactions of
electrons and holes with the adsorbed molecules of oxygen and/or
ozone as well as H2O or OH
on the catalyst surface will generate
reactive hydroxyl radicals. The non-selective oxidizing attack of
* Corresponding author. Tel.: þ49 30 6392 5652; fax: þ49 30 6392 5654.
E-mail addresses: m.mehrjouei@yahoo.com, meh@btu-lc.fta-berlin.de
(M. Mehrjouei).
lutants in water results in decomposition and mineralization of
these compounds.
Due to its low toxicity and costs, commercial availability,
chemical inertness and high photoconductivity, utilization of TiO2
in the anatase form as a photocatalyst was reported for oxidation
and removal of numerous chemical compounds such as pollutants
in water and air (Khataee et al., 2011; Bahnemann et al., 2002;
Sekiguchi et al., 2010). TiO2 is involved in advanced oxidation
treatment methods in two forms; suspended in aqueous solutions
for slurry applications (Puma and Yue, 1998; Puma et al., 2007) or
immobilized on stable substrates (Shephard et al., 2002). Due to the
better mass transfer properties of slurry systems compared with
immobilized photocatalyst systems, this form of application is still
interesting for many researchers. However, further TiO2 filtration
from treated wastewaters and photocatalyst recycling steps in
suspension systems restricts the use of this form of application to
laboratory experiments only.
Immobilization of the photocatalyst on supports solves this
problem and, for this reason, use immobilized-TiO2 seems to be
more feasible for practical purposes. In this way, the reactor design
plays a significant role in the improvement of the weak mass
transfer conditions of fixed TiO2. Several immobilization techniques
(Mills et al., 2002; Habibi and Nasr-Esfahani, 2007; Chen et al.,
2008; Peralta-Hernandez et al., 2007) and various materials as
supports for the photocatalyst have been reported (Faramarzpour

0301-4797/$ e see front matter Ó 2013 Elsevier Ltd. All rights reserved.
http://dx.doi.org/10.1016/j.jenvman.2013.02.021
 M. Mehrjouei et al. / Journal of Environmental Management 120 (2013) 68e74 69

et al., 2009; Sun et al., 2008; Matsuzawa et al., 2008; Hidalgo and Solution inlets
Bahnemann, 2005).
In the present study, a new structure of falling film reactors has
O3 Outlet
been designed and developed for advanced water treatment pro-
cesses. The three-phase falling film reactor combines a UVA-
irradiation source, immobilized TiO2 as solid phase, water or
wastewater as liquid phase and oxygen or/and ozone as gas phase in
optimum conditions, providing different application possibilities for
heterogeneous oxidation systems. Photocatalytic oxidation (TiO2/
Falling film
UVA/O2), photocatalytic ozonation (TiO2/UVA/O3), photo-ozonation
(UV/O3), catalytic ozonation (TiO2/O3), photo-Fenton oxidation
(Fe3þ/UVA/H2O2), photocatalytic Fenton oxidation (TiO2/UVA/Fe3þ/ 26 mm
H2O2), etc. are examples of the advanced oxidation techniques Inner tube 64 mm
which can be handled on demand by using this falling film reactor.
Oxalic acid was chosen as the model compound for evaluation of
Immobilized
the photocatalytic activity of immobilized TiO2 in this work. This TiO2 particles
compound is a detectable intermediate in the mineralization of
many pesticides and other organic compounds (Devipriya and 700 mm
Yesodharan, 2005; Herrmann et al., 1999) and, at the same time, UVA lamp
it is oxidized directly to CO2 without the formation of any stable
intermediate products (Mehrjouei et al., 2011; Addamo et al., 2005).
Outer tube
2. Experimental details

2.1. Reactor design and setup details

Ozone movement
direction
Fig. 1 shows the schematic structure of the falling film reactor. A
borosilicate glass tube is fixed coaxially inside another bigger tube
from borosilicate glass by using two aluminum caps, surrounding
the UV light source. TiO2 particles were immobilized on the outer
surface of the inner tube and on the inner surface of the outer tube.
Thus, the annular space between two tubes is used as a reaction
medium. In this design, the wastewater is injected into the reactor
through small apertures in the upper cap to form thin liquid falling
Stand
films over the walls of tubes. The wastewater leaves the reactor
from the bottom cap to be transferred into a storage container and Solution outlet
then to be recycled again to the inlet point of the reactor. Two O3 inlet
membrane pumps recycle the wastewater through the reactor over
the inner and outer tubes separately. Simultaneously, the gas flow Fig. 1. The structure of the falling film reactor.
is being imported through a separate gas inlet on the bottom cap to
move through the space between the two tubes and leave the Nitric acid (65%, Merck, Germany) and ethanol (>99.8%, Chem
reactor at the top gas output. Therefore, in the operation conditions solute, Germany) were used in the preparation of the TiO2 sus-
of the falling film reactor, an optimum status is provided for ab- pension for immobilization on borosilicate glass.
sorption of oxygen or ozone molecules into the falling films of The dark brown solution used in determining the distribution
wastewater as well as for adsorption of these molecules and pattern of liquid falling films was prepared by ozonation of a
pollutant molecules in wastewater on the surface of photoexcited saturated potassium iodide solution.
fixed-TiO2 particles. More technical specifications of the falling film
reactor are given in Table 1. 2.3. Measurements
A Narva Lichtquellen GmbH & Co., Germany, KG, LT 30 W/009
UV lamp with a range of wavelengths between 300 nm and 420 nm The concentration of ozone in the gas phase was determined by
and a pronounced maximum wavelength of about 360 nm was used an ozone analyzer model RT1 produced by Anseros Ozomat GM,
as the irradiation source. The incident light intensity of this source Germany. The ozone concentration in the aqueous phase was
was ca. 1 mW/cm2. An illumination spectrum of the UVA irradiation measured by the indigo method (Bader and Hoigne, 1981).
source produced by the manufacturer is shown in Fig. 2. The concentration of oxalic acid was measured by ion chroma-
An ozone generator model OZ 502/10 supplied by Fischer, Ger- tography using the Dionex DX 500 with conductivity detection
many produced ozone from pure dry oxygen (Air Liquide, >99.5
Table 1
vol.%, H2O <200 ppmv) on demand. The technical specifications and operation conditions of the falling film
reactor.
2.2. Materials
Glass tubes length 70 cm
Glass tubes diameters 2.6 cm and 6.4 cm
2
Degussa P-25 TiO2 (BET surface area 50 m /g, 30 nm mean Tubes wall thickness 0.2 cm
particle size) was used throughout this work as the photocatalyst. Internal volume ca. 1.8 L
Analytical grade of oxalic acid was purchased from Merck Active surface area ca. 200 cm2
Liquid falling rate 100e400 mL/min
(Germany) to be used as the model compound for catalytic or Gas flow rate 10 L/h
photocatalytic treatment.
70 M. Mehrjouei et al. / Journal of Environmental Management 120 (2013) 68e74
1 aqueous falling films was calculated for each recycling rate using a
0.9
0.8
0.7
Relative intensity
0.6
0.5
0.4
0.3
0.2
0.1
0 inner and outer tubes.
200 250 300 350
wavelength, nm
Fig. 2. Illumination spectrum of UVA irradiation source.
connected to an Ion Pac AG4A (guard column) and an AS14 anion
exchange column with a 4 mm format (Dionex). The flow rate of the
mobile phase, NaHCO3 (1.7 mM)/Na2CO3 (1.8 mM), was fixed at
1.2 mL/min.
The UVA-light intensity was measured using a UVA-light sensor
produced by Gerus mbH, Germany.
2.4. TiO2 immobilization
In addition to borosilicate glass as support material for immo-
bilization, TiO2 particles were also immobilized on PMMA by using
a different fixing procedure.
The immobilization process on borosilicate glass tubes was
performed by an efficient and simple technique developed by
Netherlands Energy Research Foundation (ECN) researchers for
deposition of TiO2 particles on a quartz sheet of solar cells (Hosseini
et al., 2007). In this method, the suspension of TiO2 with 1% solid
content of TiO2 in mass was prepared by dispersing 15 g of P-25
Degussa into a mixture of 1125 g of absolute ethanol and 375 g of
nitric acid (ca. 2 M). Existence of nitric acid in the suspension gua-
rantees an adequate dispersion of stabilized TiO2 colloids (Marugan
et al., 2009). Before the coating process, the suspension was ultra-
sonicated for 15 min. For dip-coating, the suspension was loaded
into the space between two glass tubes and it was discharged from
the bottom outlet of the reactor at a constant rate of 10 cm/min. The
loading and discharging processes were repeated 5 times in order to
obtain a uniform thin layer of TiO2 over the surface of the glass tubes.
Then, the tubes were annealed at 450  C for 30 min.
TiO2 immobilization on PMMA tubes was performed using
special binders. The full immobilization procedure will be probably
published later in a separate paper. It has to be mentioned that the
surface wettability of TiO2 immobilized on PMMA was observed to
be less than that on BSG.
2.5. Average thickness of the liquid falling films
The laminar thickness of liquid falling films is not constant along
the vertical tubes. Rogers (1981) described the thickness of falling
films as a function of Reynolds number (Re) and Archimedes
number (Ar) at any position on the horizontal tubes. Determination
of the falling film’s thickness at any point of the reactor walls re-
quires mathematical calculations that are out of the scope of the
present paper. Therefore, in this study, an average thickness of
simple approach as follows:
For each recycling rate, water was recycled through the reactor
for 5 min in order to reach the steady state conditions of the
membrane pump. Then the pump was switched off to interrupt the
water injection into the reactor inlet. Just after injection was
interrupted, the out-coming water from the reactor outlet was
collected and weighed. The process was repeated three times and
the average amount of water at each recycling rate was calculated.
By plotting the average volumes of water vs. recycling rates,
intercept was computed as the remaining amount of water in the
connection pipes and it was subtracted from the average volumes.
Finally, the average thickness of the falling film was obtained by
dividing the average volumes of water by the surface area of the
reactor wall. The measurements were separately performed for the
400 450
2.6. Distribution of the liquid falling films
The superhydrophilicity of TiO2, which was well described by
Vormoor (2009), provides high wettability of surfaces coated with
TiO2 particles after UV illumination. This phenomenon is an
essential factor for effective photocatalytic treatment of aqueous
solutions. In order to evaluate the distribution of liquid falling films
over the reactor walls, a simple technique was employed based on
measurements of UVA-light absorption using a UVA-light sensor. In
this technique, a hypothetical thin strip was determined around a
circle of the tubes. Four different positions were chosen around the
strip circle (three o’clock, six o’clock, nine o’clock, and twelve
o’clock). The UV-light sensor was fixed on these four positions at a
right angle to the reactor wall.
A dark brown ozonized potassium iodide solution was prepared
as the falling liquid and two different liquid falling rates of 100 mL/
min and 200 mL/min were chosen for this assessment.
The UVA-light absorptions at different liquid falling rates and
different positions were calculated using Equation (1):
I0
I
A ¼ (1)
I0
where A is the UVA-light absorption, I0 is the UVA-light intensity at
each position in the absence of liquid falling films and I is the UVA-
light intensity during the falling of liquid films. In this technique,
the UVA-light absorption at each position and recycling rate in-
dicates the relative thickness of liquid falling films at those
conditions.
2.7. Gas absorption into the liquid falling films
The absorption of gas molecules into water or wastewater is a
vital step in the heterogeneous photocatalytic treatments.
Depending on the water purification method used, ozone and/or
oxygen must first be dissolved in water to undergo the heteroge-
neous oxidationereduction reactions on the active surface of
photocatalyst. In order to evaluate the absorption level of ozone
into the liquid falling films, two sets of experiments were per-
formed under two different operation conditions (modes) of falling
film reactor. First, a set of experiments was established using
single-pass mode. In these operation conditions, appropriate
amounts of fresh deionized water were continuously injected into
the upper inlet point of the reactor producing liquid falling films in
the presence of a counter permanent flow of ozone-oxygen gas
mixture ([O3] ¼ 135 mg/LO2 ). Two different liquid falling rates of
100 mL/min and 400 mL/min were chosen to be investigated in this
section. Under these operation conditions, the deionized water
 M. Mehrjouei et al. / Journal of Environmental Management 120 (2013) 68e74 71

passed through the reactor only once and the ozone concentration tubes, all other investigations were performed using just the
in the out-coming water was measured at 10 min intervals. Next, immobilized photocatalyst on borosilicate glass tubes.
attempts were made to assess the influence of the recycling rate on
the ozone absorption level into the liquid falling films. For this 3.1. Distribution of liquid falling films
purpose 500 mL of deionized water was constantly recycled
through the reactor countering the gaseous flow of ozone-oxygen Fig. 3 shows the distribution pattern of liquid falling films on the
with ozone content similar to what was used in the single-pass corresponding surface of outer and inner tubes in the operation
mode. Recycling rates of 100 mL/min and 400 mL/min were also conditions of the falling film reactor using two different recycling
selected for this section of the present study. The ozone concen- rates of water. In this figure, each point reflects the relative thick-
tration in the recycled water was measured at 10 min intervals. The ness of the liquid falling film at four different positions and using
measurements were repeated twice and an average of two readings two different falling rates. Due to the smaller diameter of the inner
was reported as the result for each case. tube comparing to that of the outer one, the thickness of falling
films on the inner tube is greater than that of the outer tube at both
solution recycling rates. It can be clearly seen that higher recycling
2.8. Ozone decomposition on the photocatalyst surface by UVA
rates led to thicker and more uniform thickness of liquid falling
irradiation
films.
This set of experiments was performed in order to find the in-
3.2. Average thickness of liquid falling films
fluence of irradiation on the decomposition of ozone molecules in
the presence of immobilized photocatalyst inside the falling film
Fig. 4 plots the average thickness of liquid falling films vs. the
reactor. For this aim, a stream of ozone-oxygen gaseous mixture
liquid recycling rates. Solution recycling rates between 50 mL/min
was constantly flowed into the reactor and ozone concentration in
and 200 mL/min were chosen for this assessment. It can be seen
the gas phase was continuously measured at the output of the
that, due to the bigger diameter and surface area of the outer tube
reactor. After reaching steady state conditions of ozone concen-
compared with those of the inner one, the average thickness of
tration in the gas phase, the irradiation source was switched on.
liquid falling films over the surface of the inner tube is greater than
The measurement of ozone concentration was done over a period of
that over the surface of outer tube at all recycling rates. According
70 min under irradiation conditions. After this step, the irradiation
to these results, the average thickness of falling films varies from
source was switched off and the measurement of ozone was fol-
about 40 mm to about 150 mm depending on the solution recycling
lowed in the dark. The investigation was performed for four
rate.
different ozone concentrations between 60 m/L and 180 mg/L. This
evaluation was done in the absence of liquid falling films.
3.3. Photoactivity of immobilized TiO2

2.9. Adsorption of model compound on the immobilized TiO2
The adsorption of oxalic acid as a model compound on the
immobilized photocatalyst was investigated at the natural acidic
pH of oxalic acid solutions (measured pH ¼ 2.5e3) at 25  C. Solu-
tions of oxalic acid with concentrations of 0.5 mM and 2.5 mM were
prepared for this purpose. Firstly, the surface of fixed TiO2 inside
the falling film reactor was washed with deionized water and was
dried by hairdryer. After reaching ambient temperature, 500 mL of
oxalic acid solutions was injected into the reactor and was recycled
in darkness for a duration of 4 h. At one hour intervals, sampling
was performed in order to measure the concentration of oxalic acid
in the solution. The adsorption of oxalic acid on the catalyst surface
was calculated using the following equation (Equation (2)):
The photoactivity of immobilized TiO2 on the walls of the falling
film reactor was evaluated for the oxidation of oxalic acid in
aqueous solutions. Degradation of oxalic acid was separately per-
formed on the surface of fixed TiO2 on PMMA tubes and BSG tubes.
Three different oxidation systems were involved in the assessment
and the results are shown in Fig. 5. It can be clearly seen that the
photoactivity of immobilized TiO2 on BSG is higher than that on
PMMA for both photocatalytic oxidation (TiO2/UVA/O2) and pho-
tocatalytic ozonation (TiO2/UVA/O3) systems. An almost complete
removal of oxalic acid was obtained after about 50 min of photo-
catalytic ozonation using immobilized photocatalysts on borosili-
cate glass tubes, whereas a period of 100 min was required for this
Position A

C0
C
X ¼ (2)
S

where X is the adsorption level of oxalic acid on the catalyst, S is the

surface area of the immobilized catalyst and C0 and C are the initial
concentration of oxalic acid and the concentration of oxalic acid in
samples after the recycling time respectively. In fact, the decrease of
Position D Position B
concentration over the investigation time was attributed to the
adsorbed amounts of oxalic acid on the catalyst surface. The mea-
surements were repeated three times. An average of the decrease of
oxalic acid concentration in the aqueous solution at each sampling
divided by the surface area of the reactor walls was reported as the
adsorption level of oxalic acid.

3. Results and discussion

Position C

Except for the photoactivity experiments which were done Fig. 3. Distribution pattern of liquid falling films on the outer tube (white) and inner
comparatively using fixed TiO2 on borosilicate tubes and PMMA tube (black) at solution recycling rates of 100 mL/min (B) and 200 mL/min (,).
72 M. Mehrjouei et al. / Journal of Environmental Management 120 (2013) 68e74

180 treatment of various types of wastewaters in the falling film reactor.

The durability of the immobilized photocatalyst on the reactor
160
walls was evaluated by a comparison between the photoactivity of
Average thickness of falling film, µm

140
120
100
80
60
40
20
0 washing of poorly fixed TiO2 from the surface, as well as to the
50 100 150
Recycling rate, mL/min
Fig. 4. The average thickness of liquid falling films vs. solution recycling rate over the
surface of the inner tube (light) and outer tube (dark).
purpose using immobilized photocatalysts on PMMA tubes.
Application of photocatalytic oxidation systems led to degradation
efficiencies by about 49% and 76% after 100 min using fixed TiO2 on
PMMA and borosilicate glass tubes respectively. However, the low
degradation efficiency of oxalic acid using catalytic ozonation sys-
tems was observed to be not dependent on the support and the
type of immobilized catalyst. This indicates that adsorption of
oxalic acid molecules on the catalyst surface does not promote the
degradation of oxalic acid by ozone molecules under the operation
conditions of the falling film reactor.
The decreased photoactivity of fixed photocatalyst particles on
PMMA compared with that on borosilicate glass can be firmly
attributed to the low surface wettability of immobilized TiO2 on
PMMA supports. Low surface wettability decreases the effective
interaction between molecules of pollutants in the water and the
active oxidizing reagents on the surface of the photocatalyst and as
a consequence, it influences negatively the efficiency of oxidation.
3.4. Durability of immobilized TiO2
The abrasion and gradual removal of immobilized TiO2 in
addition to the poisoning effects probably happens during the
1
0.9
0.8
0.7
Concentration, C/C0
these photocatalysts before and after a certain period of time. With
this aim, the performance of two different advanced oxidation
processes in decomposition of oxalic acid was investigated on a
freshly immobilized photocatalyst (Fig. 6, t ¼ 0). Later after 10
months and handling approximately 200 h of several oxidation
processes dealing with many compounds on the same immobilized
photocatalyst, oxidation of oxalic acid was repeated under similar
experimental conditions (Fig. 6, t ¼ 200 h).
The results in Fig. 6 indicate that after 200 h working time of the
falling film reactor, a decrease of about 15% on average was
observed for the efficiency of photocatalytic oxidation of oxalic
acid. This decrease could be mainly attributed to the removal and
200
poisoning of the good fixed photocatalyst particles over the time.
However, this decrease in the efficiency was much lower for pho-
tocatalytic ozonation, highlighting the strong influence of ozone in
the oxidation process, which can effectively cover this fatigue. It
must be added that washing the immobilized catalyst’s surface by
using nitric acid solutions (0.1 M) has greatly refreshed the pho-
toactivity. This fact highlights the role of poisoning effects on the
decrease of catalyst photoactivity.
3.5. Absorption of ozone into liquid falling films
As expected, Fig. 7 shows that the average concentration of
ozone in water in the recycling mode conditions is higher than that
in single mode conditions due to longer contact time between
ozone molecules and recycled water. The results in Fig. 7 show that
in recycling mode conditions, an increase of the recycling rate from
100 mL/min to 400 mL/min causes no remarkable change on
average in the absorption level of ozone in water. Under these
conditions, the ozone concentration in the liquid phase reaches
almost constant value after a short time; however, it is clear that in
the case of lower recycling rates, a relatively longer time is expected
to achieve the saturation level of ozone in water.
Under single-pass mode conditions, increasing the falling rate
from 100 mL/min to 400 mL/min decreased the ozone concentra-
tion in water by about 3 mg/L on average (Fig. 7). This effect can be
1.0
0.9
0.8
0.7
Concentration, C/C0

0.6
0.6
0.5
0.5
0.4
0.4
0.3
0.3
0.2
0.2
0.1
0.1
0.0
0 0 20 40 60
0 20 40 60 80 100
Process time, min
Process time, min
Fig. 6. Degradation of oxalic acid (1 mM) by photocatalytic oxidation (,) and pho-
Fig. 5. Degradation of oxalic acid (1 mM) in TiO2/O3 (B), TiO2/UVA/O2 (6) and TiO2/ tocatalytic ozonation (B) oxidation systems at t ¼ 0 h (white) and t ¼ 200 h (black) of
UVA/O3 (,) systems by using immobilized TiO2 on BSG (black) and PMMA (white), the age of immobilized catalyst, recycling rate ¼ 100 mL/min, solution
recycling rate ¼ 150 mL/min, solution volume ¼ 500 mL, T ¼ 25  C, pH ¼ 2.8. volume ¼ 400 mL, T ¼ 25  C, pH ¼ 3.5.
 M. Mehrjouei et al. / Journal of Environmental Management 120 (2013) 68e74 73

40 Table 2
Adsorption level of oxalic acid on the immobilized TiO2 (mg/cm2).
Ozone concentration in liquid falling films, mg.L-1

35 Time C0 ¼ 0.5 mM C0 ¼ 2.5 mM

After 1st hour 6.19 14.77
30
After 2nd hour 6.80 15.46
After 3rd hour 7.37 16.59
25 After 4th hour 7.85 17.64

20
for all the investigated concentrations of ozone, an almost constant
15 ratio of the initial concentration (about 37  2%) was decomposed
during the illumination time.
10 The adsorption of ozone molecules on the photoexcited surface
of the immobilized photocatalyst and their reactions with the
5
photogenerated electrons thereon is the main reason for the
decrease of ozone concentration in the gas phase (Reactions 1e3).
0
0 10 20 30 40 50 60
O3 þ e
/ O



3 Reaction 1
Time, min

Fig. 7. Ozone absorption level in the liquid falling films, recycling mode (black) and 
O
þ 
3 þ H / HO3 Reaction 2
single-pass mode (white) for falling rates of 100 mL/min (,) and 400 mL/min (B), gas
flow rate ¼ 10 L/h, T ¼ 25  C.
 
HO3 /O2 þ OH Reaction 3

explained by the difference in thickness of the liquid falling films at All active radicals produced during this process can attack the
two different falling rates. Thinner falling films of water at a falling pollutant molecules which are adsorbed on the catalyst surface to
rate of 100 mL/min provide a higher surface to volume ratio of oxidize and decompose them gradually. However, hydroxyl radicals
water in contact with ozone molecules compared with the thicker are the most important oxidizing reagent available in the reaction
falling films of water at 400 mL/min. medium (Agustina et al., 2005).
Summarizing, the high level of ozone absorption which was
observed in the single-pass mode and its slight difference from that 3.7. Adsorption of the model compound on immobilized TiO2
of the recycling mode indicate that gas absorption in the liquid
falling films occurs rapidly in the operation conditions of the falling The adsorbed amounts of oxalic acid as model compound on the
film reactor. However, in the single-pass mode operation condi- catalyst surface over the investigation time are shown in Table 2. It
tions, the surface to volume ratio of the falling films seems to be an was clearly observed that increasing the oxalic acid concentration
important factor determining the absorption level of ozone into the in the aqueous solution increased its adsorption level on the cata-
falling films. lyst surface. Furthermore, due to the increase of the adsorption
level over time, it seems that the equilibrium between the adsorbed
3.6. Illumination effect on ozone decomposition molecules on the photocatalyst surface and the molecules in the
diffusion layer after 4 h was not yet established, and a longer time
According to the results presented in Fig. 8, ozone molecules was required to reach the equilibrium point.
inside the reactor were decomposed by irradiation of UVA light.
Fig. 8 shows that the level of ozone decomposition has a correlation 4. Conclusions
with the initial content of ozone in the gas mixture; so, a higher
initial concentration led to higher ozone decomposition. However, Considering the design benefits of the falling film reactor
developed in this study, including simplicity, effectiveness, multi-
200 functionality, good mass transfer properties, etc., it can be an
180
attractive applicable option to the treatment of different types of
pollutant water or wastewaters. In the operation conditions of the
160 falling film reactor, three important factors (photo-induced semi-
Ozone concentration, mg.L-1

140 conductor surface, wastewater and ozone/oxygen molecules) are

brought much closer to each other. In this way, an optimized and
120 yet not complicated condition will be available for a combinatory
100 and synergistic oxidation of target pollutant molecules existing in
the wastewater. The design of the falling film reactor is suitable for
80 handling different advanced oxidation processes.
60 The photoactivity of immobilized TiO2 on the reactor walls was
observed to be remarkable. The ozone’s existence in the photo-
40
catalytic treatment caused a complete degradation of oxalic acid
20 Dark UVA illumination Dark
after about 50 min and handling the photocatalytic treatment in
the presence of oxygen led to about a 65% decrease in the initial
0
0 15 30 45 60 75 90 105 120 135 150
concentration of oxalic acid at the same time. The wettability of the
TiO2 surface is a vital factor for a sufficient heterogeneous photo-
Process time, min
catalytic treatment.
Fig. 8. The effect of UVA irradiation on decomposition of ozone in the gas phase, gas An adequate distribution of the liquid falling films over the
flow rate ¼ 10 L/h, T ¼ 25  C. reactor walls was observed. Depending on the liquid falling rate,
74 M. Mehrjouei et al. / Journal of Environmental Management 120 (2013) 68e74
the average thickness of the falling films has been varied from
about 40 mm to about 150 mm.
The ozone absorption into water was on average between
25 mg/L and 35 mg/L depending on the operation mode of the
falling film reactor and the falling rate of the solution.
Due to the reaction of ozone with photogenerated electrons on
the photocatalyst surface, the UVA illumination decreased the
initial ozone concentration in the gas phase by about 37%.
The adsorption level of oxalic acid on the immobilized photo-
catalyst was increased by increasing the concentration of oxalic
acid in the solution.
Acknowledgments
This work was funded by the German federal ministry of eco-
nomics and technology (BMWi) according to the decision of the
German parliament.
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