DESALINATION

ELSEVIER
Desalination 156 (2003) 193-I 97
www.elsevier.com/locate/desal
Treatment of synthetic industrial wastewater with UV/TiO, and
RO using benzene as a model hydrocarbon
Nader M. Al-Bastaki
Department of Chemical Engineering, College of Engineering, University of Bahrain, I? 0. Box 32038, Bahrain
Tel. +973 782122; Fax +973 684844; email: naderbsk@eng.uob.bh
Received 17 February 2003; accepted 21 February 2003
Abstract
Contamination of water resources with hazardous chemicals is one of the main concerns of all private and public
sectors involved in the water production for drinking, irrigation and domestic use. The conventional disinfection
process using chlorination adds to the complexity of the problem as some of these chemicals are precursors for
disinfection by products such as trihalomethanes. This paper describes the work done to study the eff%ziency of two
types of processes in removing a model hydrocarbon, namely, benzene, which was added to water at a concentration
of 100 ppm. The two processes investigated were RO and UVITiO,. The RO process was based on a FilmTec SW30
spiral wound membrane, which was operated at pressures of 20,40 and 60 bar. The UV/TiO, employed was PhotoCat,
manufactured by Purifies, Canada. The heart of the PhotoCat unit was 32 low pressure, low intensity mercury vapor
lamps connected in series. Gas chromatography was used to analyze the results. The results showed that the UV/
TiO? resulted in a removal of 99.28%. However, the RO performance was less impressive with amaximum separation
of 82.3%. At 40 bar, a negative permeability was observed, as the concentration of benzene in the permeate was
higher than the feed. This latter result shows that care has to be taken with hydrocarbons polluting the feed water to
RO units, since in certain cases the product water will more polluted than the feed.
Keywords: UVITi02: RO; Wastewater treatment; Permeability; pH
1. Introduction
Many concerns have been expressed recently
with respect to the traditional drinking water and
wastewater treatment processes, which have
encouraged the consideration of alternative or
modified processes. One of these concerns is the
formation of disinfection by-products (DBPs),
particularly, trihalomethanes (THM) which may
result due to the reaction of chlorine with the
Presented at the European Conference on Desalination and the Environment: Fresh Water for All, Malta, &8 May 2003.
Ewopeau Desalination Socie@, International Water Association.
00 I 1-9 164/03/$- See front matter 0 2003 Elsevier Science B.V. All rights reserved
PII: SO01 l-91 64(03)00341-2
194 Y M. Al-Bastaki / Desalination 156 /2003) 193~-197
naturally occurring humic and fulvic acids [I].
Membrane processes, such as microfiltration
(MF) and ultrafiltration (UF), and photocatlytic
processes are possible methods of overcoming the
shortcomings of traditional water treatment
methods.
Recently, UF and nanofiltration (NF) mem-
branes have been employed in large-scale com-
mercial plants to treat surface and river water as
a replacement of the traditional methods based
on sedimentation and media filters [2,3]. More-
over, the use of MF and UF membranes for the
treatment of sewage waste water has evolved
lately, in the form of membrane bioreactors [4,5].
In addition, RO and NF processes have been
considered for the removal of herbicides and
pesticides [6,7].
An increasing number of studies have been
reported in the recent literature about the applica-
tion of UV/TiO, for the treatment of waste water.
The emphasis has been on the decomposition of
hydrocarbons [8,9] herbicides [ IO,1 I] and other
industrial wastes such as dyes [ 12,131 and heavy
metals [ 14, I 51.
2. Experimental setup and procedure
2.1. Water samples
Synthetic waste water samples were prepared
by mixing benzene with distilled water. The
concentration of benzene in all of the samples
PHOTO-
CATALYTIC
PRE
FILTER
COALESCER
REACTOR
,
ACCUMULATOR
/
/ SEPARATION
was 100 ppm. The concentration of the samples
was measured using a CC with a thermal con-
ductivity detector (TCD) and an HP 3390A
Reporting Integrator.
2.2 Experimental setup
The water samples were treated with two
different processes, namely? reverse osmosis (RO)
and UVITiO,. Each process utilized small scale,
industrial elements. The membrane process (RO)
was operated manually while the lJVITi0,
process was a fully automated small pilot scale
plant and could be operated either manually or
by a computer.
The UV/TiO, apparatus used in this work was
a PhotoCat unit manufactured by Purifies, Canada.
The unit is a small scale mobile pilot plant, located
at the Research Deanship laboratory, University
of Bahrain. The process utilizes TiO, catalyst
powder suspended in water. A schematic diagram
of the process is shown in Fig. I. The reactor
section employs 32 quartz tubes, which generate
UV light at a wavelength of 365 nm. The total
added length of the low pressure UV lamp tubes
is 48 m. The water flow rate is adjustable up to
12 I/min. The effective volume ofthe liquid within
the reactor, which is exposed to UV, is about
3.77 I. An inlet pre-filter removes large suspended
solids while a coalescer is used to remove oil and
grease. A dedicated ceramic filter separates the
catalyst fi-om the suspension after exposure to UV.
SLURRY
FEED
PUMP
Fig. I. Schematic diagram of the PhotoCat UV/Ti02
photocatalytic reactor.
N.M. Al-Bastaki / Desalination 156 (2003) 193-197 195
A 1 HP compressor is employed to compress
air to 8.5 atm. The compressor periodically gene-
rates a pressure pulse within the system to remove
the catalyst from the ceramic filter and other parts
within the system to keep it always in suspension.
The compressed air in combination with automatic
pneumatic valves assures this operation. The accu-
mulator acts as a buffer tank and as a degassing
device and plays a function in recycling the catalyst
back to the reactor. The unit is also equipped with
pH and flow control as well as with metering pumps
for dosage of acid, base or oxidizing agents, as
required. The feed and recirculation pumps are
% HP.
Fig. 2 shows a simplified flow diagram for the
RO process. The RO unit consisted of a high-
pressure pump, a FilmTec SW30 membrane, feed
and product tanks, pressure gauges and rotameters
for flow rate measurement.
2.3. Experimental procedure
200 I of 100 ppm solution of benzene in water
was placed in the feed tank of the UV/TiO, pro-
cess. The product was recycled to the feed tank.
Samples of the product were taken for analysis
every 15 min. To study the effect of pH, experi-
ments were also done at various pH values by
adjusting the pH of the feed and monitoring the
FEED TANK
IRESSURt
PUMP
-i I
k ROTOMl;TtR
/
L-l
1 PRESSURt GAUGb
CONCENTRATE
(RETENTATE)
TANK
Fig. 2. Schematic diagram of the RO unit.
online pH measurement until a steady pH was
obtained.
The RO process was operated at three pressures,
namely, 20 bar, 30 bar and 60 bar. Samples of the
permeate were taken for analysis of the concen-
tration, and the permeate flux was measured using
a rotometer as well as manually using a graduated
cylinder and a stop watch.
3. Results and discussion
Fig. 3 presents typical GC outputs showing
water and benzene peaks.The UV/TiO, photo-
catalytic process is generally believed to be
effective for treatment of hydrocarbons. The
results shown in Fig. 4 appear to agree with this
notion. The percent removal of benzene was
calculated by measuring the concentration of
benzene at various intervals, up to 45 min. The
benzene concentration in the permeate was steady
after I5 min of reticulation, with a removal
percentage of about 99.28%. The production of
CO, as a result of the oxidation reaction results
in lowering the pH of the solution as can be seen
in Fig. 5.
In the UV/TiO, process, UV light supplies energy
to the TiO, catalyst and prompts the transport of
an electron from the valence band to the con-
ductive band producing a positively charged hole
in the catalyst. The free electron is taken up by
oxygen molecules to create superoxide radicals.
The superoxide radicals react with the water
molecules to produce hydroxyl radicals. Similarly,
at the positive holes water molecules or hydroxyl
ions are oxidized to produce additional hydroxyl
radicals. The organic matter is oxidized at the
catalyst surface and in the solution by any of the
following routes: the hydroxyl radicals, the
superoxide radical, direct oxidation of adsorbed
organics at the positive holes or by the conductive
band electron [16].
The benzene removal efficiency of RO appears
to be less pronounced compared to the UV/TiO,
as shown in Fig. 6. The maximum separation was
196 !V .Af. .dl-Bastaki IT Desalination 156 (2003) 193 197
Fig. 3. Typical CC output. This specific result was for the
test using RO. The sharp peak represents benzene.
1000
E
E
- 100 ppmf eed
5 100
. -
5
z
8 10
s
0
zi
:
m 1
2
_/
i i i
0. 1
0 10 20 30 40 50
Time, min
Fig. 4. Concentration of benzene after treatment with UV/
TiO
,.
observed at 30 bar with a permeate concentration
of 17.7 ppm or a removal of 82.3%. The results
indicate that the rejection of benzene by the poly-
amide composite SWRO FilmTec membrane varies
with pressure. Negative permeability is noticed
at a pressure of 20 bar. This is indicated by an
increase in the concentration of benzene in the
9.0
8.8
8. 6
I
a
a. 4
a. 2
8. 0
I-
4
0 I O 20 30 40 50
Time, min
Fig. 5. pH change with UV/TiOz treatment.
0 10 20 30 40 50 60 70
P, bar
Fig. 6. Concentration of benzene in the permeate for
different pressures of RO treatment.
permeate compared to the feed. The permeate
flux, however, followed a linear trend with
increasing pressure, as shown in Fig. 7. Due to
the very low concentration of benzene in the feed
water, the nonlinear flux of benzene with pressure
has apparently not affected the linearity of the
water flux vs. pressure curve.
4. Conclusions
The UV/TiO, photocatalytic process showed
a much higher efficiency than RO in removing of
N.M. Al-Bastaki /Desalination 156 (2003) 193-197 197
1. 4e- 5
1. 2e- 5
Y l . Oe- 5
2
& 8. 0e- 6
6. 0e- 6
4. 0e- 6
. 100ppmbenzene
- hear regression
/
10 20 30 40 50 60 70
P, bar
Fig. 7. Variation ofthe permeate flow rate with RO pressure.
traces of benzene from the feed water. The maxi-
mum removal rate was 99.28% for the UV/TiO,
compared to 82.3% for RO. Moreover, the RO
process showed a negative permeability at an
operating pressure of 20 bar, resulting in a higher
concentration of benzene in the permeate compared
to the feed.
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