PORTABLE TRIO EFFECT WATER TREATMENT SYSTEM

Ghazi Faisal Najmuldeena; Hayder A. Abdul Baria; Ali Abdul RahmanAl Ezzia,b
a
Faculty of Chemical & Natural Resources Engineering, Universiti Malaysia Pahang
Pahang, MALAYSIS
b
Department of Chemical Engineering, University of Technology,
Baghdad, IRAQ
E-mail: ali_alezy65@yahoo.com

ABSTRACT
The present study relates to a method of removing oxygenate compound
from oxygenates contaminated water and a system of particularly
combination of processes of air stripping, oxidation, inverse fluidization and
adsorption for removing oxygenate compound from oxygenates
contaminated water. In conclusion, the combination of processes such as air
stripping, oxidation occurred within the combination of inverse fluidized and
internal loop airlift reactor has achieved higher percentage removal of MTBE
in synthetic wastewater. Furthermore, the surface contact time between
MTBE molecules and hydrogen peroxide ion (H 2O2) and granulated activated
carbon (GAC) by circulation a wastewater in the combination of inverse
fluidized and internal loop airlift reactor increases percentage removal of
MTBE by oxidation and adsorption processes to reach 90%. The results
indicated that the optimum molar ratio between MTBE and hydrogen
peroxide is 1:20 with air flow rate at 7 L/min having the best performance to
remove MTBE from the synthetic wastewater.

Keywords: New design, air loop reactor, hydrogen peroxide, granular

activated carbon, methyl tert-butyl ether.

1. Introduction

Water and wastewater processing technologies become increasingly

important with diminishing natural water resources, the gradual increase of
chemical pollutants in aqueous systems, and the rapid growth of population
and industrial activities. Technology and design for treating industrial
wastewater can be divided into three categories: physical methods, chemical
methods, and biological methods. Physical treatment methods include
sedimentation, flotation, filtering, stripping, ion exchange, adsorption, and
other process that accomplishes the removal of dissolved and undissolved
substance without necessarily changing their chemical structure. Air
stripping is difficult and requires a high air-to-water ratio (>200/1 l for 95%
removal), another report states air stripping to be effective at removing
chemical pollutants but confirms that very high air to water ratios are
necessary [1]. The cost most often the treatment of concentrated pollution
by using adsorption on activated carbon for achieving high water purification
would be excessive [2-5]. The adsorption process for methyl tert butyl ether
(M TBE) by using granular activated carbon (GAC) is undesirable and
expensive because the low affinity of MTBE towards (GAC) [6], in another
study MTBE is difficult to remove by adsorption onto GAC [7]. Chemical
methods are included chemical precipitation, chemical oxidation or reduction
and other chemical reaction that involve exchanging or sharing electrons
between atoms. Advanced Oxidation Process (AOP) is considered to be an
alternative method to chlorination. In an Advanced Oxidation Process,
chemical, electrical or radiative energy is supplied to the water matrix to
produce highly reactive oxidants, which can attack and destroy the target
compound. Usually AOPs are ambient temperature treatment processes
which are primarily based on the formation of highly reactive radicals, have
recently emerged as an important class of technologies for accelerating the
oxidation and destruction of a wide range of organic contaminants in polluted
water and air [8]. Ideally AOP systems are designed to completely mineralize
the organic contaminants of concern to CO 2 and H2O but this may require
more energy and greater chemical dosage and ultimately may prove to be
cost prohibitive in certain applications [9]. Ozone and ozone/peroxide can be
quite effective in removing pollutants from waste water; however, hazardous
bromate and biodegradable organic carbon are by products of these
processes and must be removed. Meanwhile biological treatment methods
are those that involve living organism using organic or in some instances,
inorganic, substances for food, completely changing their chemical and
physical characteristics. Many different chemicals are discharged into the
aquatic environment. Some of them are not only toxic but also partly
biodegradable; therefore they are not easily removed in biological
wastewater treatment plants. However, attempts to inoculate packed beds of
granular activated carbon with bacteria by conventional means of introducing
bacteria into the bed together with a contaminated water feed stream have
proven problematic, as the bacteria are only distributed in the entry region of
the bed and this leads to loss of performance due to plugging of the bed, flow
channelling and bypassing. Current technologies, including ozonation,
microbiological methods, and traditional activated carbon filtration are not
sufficient to remove MTBE from wastewater or drinking water[10, 11]. This
obliges us to search for alternative and new method for the degradation of
organic pollutants, either to less harmful compounds or to their complete
mineralization. Discovery of those processes is necessary for effectively
removed both existing and on-going wastes. Several modifications have been
proposed to improve the conventional airlift loop reactor, and some of them
have already been adopted. Modified airlift loop reactors include the inverse
fluidized airlift, reactors with static mixers, helical flow promoters, and
perforated draft tube; refer to Figure 1a, b, and c respectively.

(a) (b) (c)

Figure 1. Modifications of the airlift loop reactor.
 The principle of the inverse fluidized bed utilizes particles with densities
lighter than the liquid phase. These particles are entrained to the down
comer against the buoyancy of the gas sparged. This inverse fluidized reactor
has been used for the biological treatment of wastewater [12, 13]. In the
process of biodegradation with the fluidized bed, the solids (microorganisms
trapped in polymeric gel) are suspended in the aqueous phase and gases in
contact with each other to provide oxygen for biodegradation. Gluz and
Merchuk [14] investigated the helical flow promoter (HFP; Figure 1c), which is
consisted of fins and baffles that were placed either on the riser or down
comer.
This caused fluid to flow in a helical pattern down the down comer as
opposed to the conventional type with straight downward flow. As the helical
flow was generated, the content of the vessel began to swirl enhancing radial
mixing in the down comer.
Cheng et al. [15] used a draft tube with perforations in an airlift reactor
to cultivate Acetobacter xylinum with an increased production level of
bacterial cellulose nanofibers as compared to the bubble column. Guo et al.
[16] used an external loop inverse fluidized bed airlift bioreactor (EIFBAB) to
treat wastewater. In this type of bioreactors gas was sparged in the middle of
the riser to aid fluidization for heavy particles in the bottom of the riser. Loh
and Liu [17] employed a similar setup in a 4 L EIFBAB (shown in Figure 2) to
eliminate high contents of phenol in wastewater.

Figure 2. The EIFBAB; external loop inverse fluidized bed airlift loop reactor.
However, a globe valve and stainless steel screen were used to prevent solid
particles from getting into the down comer. Another variation to enhance the
performance of the conventional airlift was the introduction of static mixer in
the riser. In such a vessel, liquid circulation was decreased as a result of an
increased resistance from the static mixer. Large gas bubbles were broken
into smaller ones increasing the interfacial surface for higher mass transfer
rates. Chisti et al. [18]; Potucek [19] and Gavrilescu et al. [20] have studied
the influence of the static mixer in airlift bioreactors and observed an
increase in mass transfer coefficient as compared to reactors without mixers.
Other modified types of airlift loop reactors include the convergent-
divergent airlift (Figure 3). In this type of airlift loop reactors, the draft tube
contracts and expands as the name suggests with continuous renewal of gas-
liquid interfacial area to promote mass transfer.

Figure 3. Convergent-divergent airlift loop reactor.

Mohanty et al. [21] and Li et al. [22] designed a novel multistage airlift
system consisting of three vertically staged airlift reactors constructed to
work in series (Figure 4).
 Figure 4. Multi stage airlift loop reactor.

These designs are such that there is a continuous generation of bubbles,

rupture and regeneration. This system was equipped with different spargers
(multiple orifice and single orifice) together with a screen at various stages to
encourage the continuous regeneration of bubbles.
In this study, anew design of combined stripping, oxidation, reverse
fluidized, and internal loop reactor system (SOIAAI) is used to remove (MTBE)
pollutants from drinking water. Several important parameters have been
investigated such as molar ratio of MTBE to hydrogen peroxide, air flow rate,
and residence time. The aim of this investigation was to check the feasibility
of using a new design of a combined system of stripping, oxidation, inverse
fluidized, adsorption and internal loop reactor for removal of pollutants from
wastewater.
A series of experiments were conducted to investigate the effects of
the percentage removal of MTBE from wastewater. In this experimental work,
molar ratio of MTBE to hydrogen peroxide is 1:10, 1:15 and 1:20 with the air
flow rates is 7 L/min, 8 L/min and 10 L/min with the residence time 2 _20 min
was used to investigate its effectiveness to remove MTBE.

2. Methodology
2.1. Materials
The following chemicals were used:
 (a) Methyl tert-butyl ether (MTBE) pollutants. MTBE (C5H12O with a
molecular weight = 88.15) with purity greater than 99.8% dissolve in
the pure water to produce synthetic wastewater. MTBE supplied by
chemical material store in the laboratory of (UMP) was employed as
adsorbate.
(b)Hydrogen peroxide (H2O2) as oxidation agent with 30% concentration in
volume/volume. H2O2 supplied by Wellmex Sdn. Bhd. Company and
made in Thailand.
(c) Granular activated carbon (GAC) as adsorbent is having a particle size,
18-30 mesh fraction, particle density, 0.69 g/cm 3 and density, 1.17
g/cm3. GAC supplied by company (Hamburg).

2.2. Experimental set-up

The main design of the trio-effect unit is shown in the Figures (6a-6c).
Generally the system is combination of :
1. Sripping
2. Oxidation
3. Adsorption
This system is designed,arranged and tested in an integrated mode. Figure 5
shows the flow diagram of the integrated system function as expected by the
proposed design.
 Figure 5. Flow digram of integrated system

This system comprising a combination of inverse fluidized and internal loop

airlift reactor (100) having a draft tube (110) vertically extended from a
centre of the reactor (100) and an absorbent material bed (115)
circumference the draft tube (110) with a space (120) is provided at a bottom
of the combination of inverse fluidized and internal loop airlift reactor (100).
The draft tube (110) has an opening at a first end and a second end. The
absorbent material bed is a granular activated carbon bed.
 (a)
(b)
Figure 6. Schematic diagram design of the experimental rig.

To create the space (120) between the draft tube (110) and the bottom of the
combination of inverse fluidized and internal loop airlift reactor (100), a
support (130) is fitted on the side walls of the combination of inverse
fluidized and internal loop airlift reactor (100) such that there is a distance
above the bottom of the combination of inverse fluidized and internal loop
airlift reactor (100).
To a person skilled in the art, the position of the support (130) is
adjustable to a required height for the purposes to achieve a space between
the draft tube (110) and the bottom of the combination of inverse fluidized
and internal loop airlift reactor (100). An inlet port (125) of the combination
of inverse fluidized and internal loop airlift reactor (100) for an oxygenate
contaminant water enters and hydrogen peroxide into the reactor (100).
 A dosing pump (P1) is used for providing hydrogen peroxide into the draft
tube (110) for mixing and reacting with the oxygenate compound in the
water before the inlet port as illustrated in Figure 7.

P1, Dosing waste water

Valves T1 F1 flow meter
P2 pumps tank
hydrogen
R1 regulator RE reactor C1 compressor T2
peroxide tank
nitrogen
N2 D1 distributor
cylinder

Figure 7. Schematic diagram of experimental rig design.

 During the same period, another pump (P2) is used for receiving
oxygenates contaminated water and providing oxygenates contaminated
water with hydrogen peroxide into the draft tube (110) by the inlet port.
Oxygenates contaminated water, and hydrogen peroxide are fed
continuously into the combination of inverse fluidized and internal loop airlift
reactor. The mixture oxygenates contaminated water with hydrogen peroxide
is fed to the draft tube (110) by the opening of the first end (210) in a gravity
direction of the combination of inverse fluidized and internal loop airlift
reactor.
Means for introducing air (215) into the draft tube (110) of the
combination of inverse fluidized and internal loop airlift reactor is provided to
mix with the mixture oxygenates contaminated water with hydrogen peroxide
in a counter direction. In the present study, a multi holes distributor is used
for allowing compressed air to spare at the bottom of the draft tube. Air
compressor (C1) is provided to supply the required amount of compressed air
particularly nitrogen gas into the draft tube (110) by a gas flow meter (F).
The compressed air mixed with mixture oxygenates contaminated water with
hydrogen peroxide vigorously, and this resulted air stripping and chemical
oxidation processes to occur within the draft tube (110). During air stripping
and chemical oxidation processes, the mixture oxygenates contaminated
water with hydrogen peroxide is overflow from the draft tube (110) due to the
compressed air in a counter direction. The mixture oxygenates contaminated
water with hydrogen peroxide is then directed from the draft tube (110) to
the absorbent material bed of the combination of inverse fluidized and
internal loop airlift reactor via gravity force. It is preferably that a height of
the draft tube (110) is positioned relatively higher than the absorbent
material bed such that a density difference is formed between the draft tube
(110) and the absorbent material bed for circulating oxygenates
contaminated water within the combination of inverse fluidized and internal
loop airlift reactor. With the assistance of the valves, the level of the mixture
oxygenates contaminated water with hydrogen peroxide as well as air is
maintained at a constant level within the combination of inverse fluidized and
internal loop airlift reactor.

2.3. Experimental procedure

Synthetic wastewater was used with concentration 2 ppm of MTBE. The

oxidant agent, 100 ml of hydrogen peroxide (H 2O2) was added to 8 liters of
water at 25oC in a feed box, and a granular activated carbon volume was
5072.5 cm3. The molar ratio between MTBE to hydrogen peroxide was 1:20.
During the experiments, During the experiments the density gradient between the aerated
water in the draft tube and the down-comer creat the liquid circulation at stable form and forcing
the liquid to flow downward into the annular space through granulated activated carbon (GAC)
to complete the adsorption process at the same time for completion the stripping and oxidation
processes which occur simultaneously also. The pump for synthetic wastewater tank
was maintained at 100% flow rate while the dosing pump for hydrogen
peroxide tank was maintained at 80% flow rate. The pressure was set
constantly at P (abs) = 2 bar. To achieve the steady state for the system, the
mixture of the synthetic wastewater, hydrogen peroxide and the air was run
for two hours before experiments were conducted. The treated wastewater
was collected after 1.5 hours at an outlet port of the combination of inverse
fluidized and internal loop airlift reactor. After 1.5 hours, ten samples were
collected for every 2 minutes.
 Figure 6c.Trio effect treatment scenario

These samples were analysed by UV-spectrophotometer at wavelength, 340

nm. The procedure was repeated with difference residence time at a
difference molar ratio of MTBE to hydrogen peroxide i.e. 1:10, 1:15 and 1:20
with air flow rates of 7 L/min, 8 L/min and 10 L/min and residence time of 2
-20 min respectively to investigate the effectiveness for MTBE removal. The
experiments were performed at a range of pH between 6.5 and 7.5. The
concentration of Methyl tert-butyl ether (MTBE) was determined using UV
absorbance measurements by a UV-spectrophotometer. By varies, the initial
concentrations of MTBE at 2 ppm, 1 ppm, 0.8 ppm, 0.5 ppm, 0.2 ppm to form
a standard curve plotted with the R2 = 0.980. At the wavelength of 340nm,
the UV absorbance data were collected. The removal efficiency of MTBE from
water was determined as follows:

E
Cin Ct 100
Cin

(1)

Where E is MTBE removal efficiency (%), Cin and Ct are the initial and residual
concentrations of MTBE, respectively in ppm. The pH was measured, and all
samples were collected in the cube vert for analysis. Five different initial
concentration of MTBE at 2 ppm, 1 ppm, 0.8 ppm, 0.5 ppm and 0.2 ppm were
used to plot the standard calibration curve. In addition, different wavelengths
were conducted at the range from 200 nm to 600 nm. The calibration curve is
shown in Figure 7. From the standard calibration curve, it is shown that the

y 0.542 x 0.176
linear line equation is and R2 = 0.980.

3. Results and Discussion

Figure 8 shows the effects of contact time to the percentage removal of

MTBE from synthetic wastewater. It is noticed that the percentage of removal
increases in accordance to the contact time. The percentage removal of
MTBE at 20 minutes for 2 ppm, 1.5 ppm, 1 ppm, 0.8 ppm and 0.5 ppm were
90%, 71.70%, 59.95%, 48.32% and 39.47%, respectively. For higher
concentration of MTBE in synthetic wastewater, the percentage removal is
higher as compared to the low concentration of MTBE in synthetic
wastewater. The figure also represents the impact of the effectiveness of the
removal MTBE from synthetic wastewater for three operations at the same
time which are: oxidation, stripping and adsorption processes. The features of
this new design are the absence of the possibility to knowledge the impact of
each individual process on the percentage of removal MTBE from synthetic
wastewater, but results from the subsequent experiments showed that the
removing rate of MTBE for combined processes (stripping, oxidation and
adsorption) gradually slows down after 10 min. As shown in Figure 8,
obviously, there is a two-stage for removing of MTBE. The percentage of
removal of MTBE rate within first 4 min in the first stage was higher than of
those that followed after 4 min (approximately for all types of the feed input
to the combination of inverse fluidized and internal loop airlift reactor)
because two main reasons, the first is the MTBE concentration difference
between the liquid phase (H2O) and gas phase (air) is bigger at the start of
the stripping process and between the liquid phase (oxidized water in the
draft tube) and solid phase (GAC in the annulus) in the start of the adsorption
process. This provides the highest rate of mass transfer from water to air and
from water to solid (GAC). The second reason is that the H 2O2 decomposed
very quickly to produce a large amount of OH. The produced OH can react
rapidly with organic substance (MTBE) and caused the increasing of the
oxidation efficiency of MTBE. It is noticed that the percentage of removal of
MTBE at 20 minutes for 2 ppm is 90% the reason may be due to the stable
circulation of liquid flow created by the density difference between the
oxidized liquid inside the draught tube and the liquid that in the annulus, this
step give more time to complete the stripping, oxidation and adsorption
processes in high efficiency. The impact of contact time on the percentage of
removal MTBE with different molar ratio of MTBE to hydrogen peroxide is
illustrated in Figure 9. The results showed that MTBE removing rate is
enhanced at a higher initial molar ratio of MTBE to the H 2O2 when keeping the
air flow rate
(7 liter/min) and initial concentration of MTBE (2 ppm) constants. The
percentage removal of MTBE at 20 min for molar ratios of 1/10, 1/15 and 1/20
were 75%, 80.1% and 90%, respectively.
The elimination percentage of MTBE reached approximately 90% when the
molar ratio of (MTBE/H2O2) =1/20. As shown in Figure 9. The reason may be
due to the quickly decomposition rate of (H2O2) and creating a large amount
of hydroxyl radicals which make increased in probability of attacking (MTBE)
by OH and caused the increasing of the efficiency of MTBE oxidation process.
The presented data are in Figure 10 shows the effects of contact time to the
percentage removal of MTBE from synthetic wastewater in a different flow
rates. No significant increase in the percentage of removal of MTBE from
water was recorded, is approximately constant with the contact time. The
percentage removal of MTBE at 20 minutes for air flow rate 7 liter/min, 8
liter/min, 10 liter/min are 90%, 89.6% and 89.9%, respectively.
Figure 11 illustrates the effects of contact time on the concentration with
different molar ratio of MTBE to hydrogen peroxide. It is shown that the
concentration of molar ratio of MTBE to hydrogen peroxide decreases with
contact time. It was observed that the initial MTBE concentration was
reduced at 20 min from 2 ppm to 0.2 ppm with 1/20 molar ratio of MTBE to
hydrogen peroxide. It is also observed that the concentrations at 20 min for
molar ratio 1/10, 1/15 are 0.5 ppm and 0.398 ppm, respectively.
Figure 12 illustrates the effects of contact time on the concentration of
MTBE with different air flow rates. The concentration of MTBE decreases with
time the concentrations of MTEB after 20 minutes for air flow rates 7
liter/min, 8 liter/min and 10 liter/min are 0.2 ppm, 0.208 ppm and 0.202 ppm
respectively. The results from this study, anew design of combined stripping,
oxidation, reverse fluidized, and internal loop reactor system (SOIAAI) has
showed the higher percentage removal of MTBE in synthetic wastewater
compared with conventional treatment of MTBE-contaminated groundwater.

4. Conclusions

In conclusion, the combination of processes such as air stripping, oxidation

occurred within the combination of inverse fluidized and internal loop airlift
reactor has achieved higher percentage removal of MTBE in synthetic
wastewater. Furthermore, the surface contact time between MTBE molecules
and hydrogen peroxide ion (H2O2) and granulated activated carbon (GAC) by
circulation a wastewater in the combination of inverse fluidized and internal
loop airlift reactor increases percentage removal of MTBE by oxidation and
adsorption processes to reach 90%. The results indicated that the optimum
molar ratio between MTBE and hydrogen peroxide is 1:20 with air flow rate at
7 L/min having the best performance to remove MTBE from the synthetic
wastewater. One of the advantages of the present study is that it provides a
method of removing oxygenate compound from oxygenates contaminated
water and a system thereof particularly combination of processes of air
stripping, oxidation, inverse fluidization and adsorption for removing
oxygenate compound from oxygenates contaminated water with higher
efficiency as compared to the conventional technologies. Another advantage
of the present invention is the cost of setting up system for removing is low
and less maintenance. The method of the present study produces less
hazardous compound in the water upon treatment by the system, and it is
further safe to be released to the environment.
Acknowledgments
The researcher would like to thank the Faculty of Chemical Engineering,
University Malaysia Pahang (UMP) for providing laboratory facilities to
complete this Study.
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Figure 7. Standard calibration curve at wavelength, = 340nm.
Figure 8. Effect of contact time on the percentage of removal of MTBE with
different initial concentration of MTBE.
Figure 9. Effect of contact time on the percentage of removal with different
molar ratio of MTBE to hydrogen peroxide.
Figure 10. Effect of contact time on the percentage of removal with different
air flow rates.
Figure 11. Effect of contact time on the concentration with different molar
ratio of MTBE to hydrogen peroxide.
Figure 12. Effect of contact time on the concentration with different
air flow rates.