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CHAPTER 5

SUMMARY AND CONCLUSION

5.1

GENERAL

Optimum wastewater treatment is todays challenge. However, the

use of conventional wastewater treatment processes become more
challengeable with the identification of more and more pollutants, rapid
growth of population and industrial activities, and diminishing availability of
water resources. Conventional wastewater treatment methods have been
established in removing many chemical and microbial pollutants to public
health and the environment from long time ago. However, the effectiveness of
these processes has become limited over the last two decades. Industrial
wastewaters are known to contain toxic and non biodegradable organic
substances, where biological processes are not efficient in degrading these
pollutants. Some of these organics are biorecalcitrant or inhibitory due to
enzymatic deficiencies or to their toxicological properties. For the removal of
recalcitrant organics, biological processes which are economically beneficial
cannot be chosen, but a variety of non-biological processes exist, which can
be divided into oxidative and reductive technologies.

Among all of them, advanced oxidation processes (AOPs) have

become increasingly popular in recent years as alternative or complementary
treatment. The primary use of AOPs is to degrade organic pollutants in water
by oxidation. The advantage of these processes is their destructive and nonselective nature, such that no sludge production is involved. However,

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depending on the targeted wastewater quality, extended treatment duration

may impose unaffordable high operating costs due to high energy and
chemical requirements of AOPs. A recently proposed technique to cope with
the

environmental

regulations

and

also

environmentally safer

and

economically more attractive strategy is biodegradability enhancement of raw

and biological pre-treated industrial wastewater by applying chemical
oxidative pre-treatment, in which two or three consecutive chemical and
biological processes steps are involved. Moreover, as the complete
degradation of wastewater can be hardly achieved by single treatment
method, combination of chemical and biological treatment is often the way to
optimize the overall process.

5.2

SUMMARY

In this research, an optimum operation condition for the coupled

solar photocatalytic - biological treatment processes was investigated in order
to decrease the treatment time and operational cost necessary for the
degradation of phenolic wastewater.

The wastewater samples were collected from the phenolic

wastewaters generating industries (viz. resin manufacturing, oil refinery,
paper mill, pharmaceutical and chemical industry) and characterized for
various physio-chemical parameters viz. pH, phenol concentration, COD,
BOD, chlorides and sulphates. Studies were conducted with simulated
wastewaters based on the concentration of the pollutants in the real
wastewaters.

All photocatalytic experiments were carried out at Anna University

campus in Chennai, (1300.57"N; 8014.12"E), Tamil Nadu. For Laboratoryscale studies, an open borosilicate glass trays of 1.5 L capacity was used as

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the reaction vessel. The suspensions were magnetically stirred in the dark for
30 min to attain adsorption - desorption equilibrium between phenol and
TiO2. Irradiation was carried out in the open air and continuously aerated by
a pump to provide oxygen and for the complete mixing of reaction solution.
In all cases, 1 L of reaction mixture was irradiated.

The Laboratory - scale feasibility studies had been carried out in

order to study the effects of operating parameters such as pH (3-9), catalyst
dosage (0.15 -1 g/L), catalyst reuse (15 trails), initial pollutant concentration
(10-500 mg/L), aeration (pre aeration, with and without aeration), chlorides
(50-200 mg/L), sulphates (50-200 mg/L), hydrogen peroxide (0.15-1.5 g/L),
liquid volume (0.25-2 L), solar light intensity (throughout the year) and
contact time (5 h) for degradation of phenolic wastewaters. To study the
effects of operating parameters, the experiments were conducted under the
experimental conditions of pH 6, catalyst dosage 0.25 g/L and pollutant
concentration 50 mg/L. The feasibility of degradation of phenol wastewaters
by Fixed Catalyst System (FCS) was also studied. The effect of catalyst
loading in the range of 0.15-3 g/L and reusability of FCS up to 4 trials was
studied for the degradation of phenolic wastewaters.

The Solar/TiO2 system was not effectively found to remove the

phenol concentration more than 50 mg/L. And, also the chloride and sulphate
ions gave negative effects on the phenol removal efficiency even at low
concentration of 50 mg/L. But the real industrial wastewaters contain phenol
concentration in the range of 100 500 mg/L and chloride and sulphate
concentration in the range of 50 200 mg/L. Hence, in order to accelerate the
rate of reaction, the hydrogen peroxide is used as electron acceptor. The effect
of H2O2 dosage in the range of 0.15-1.5 g/L, pollutant concentration in the
range of 100 -500 mg/L and combined effects of inorganic salts in the range
of 50 -200 mg/L was studied for the degradation of phenolic wastewaters.

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The effects of the three critical factors viz., pH, TiO2 and phenol
concentration on the photocatalytic degradation of phenolic wastewaters were
simulated and evaluated using Response Surface Methodology (RSM). This
methodology has shown to be a valuable tool to model complex process such
as the light - enhanced photocatalytic reaction and to achieve optimum
experimental parameters at minimal cost.

Four bench-scale solar photocatalytic reactors were fabricated viz.

single baffle reactor, multiple baffle reactor, cascade reactor and solar pond
reactors of 5 L capacity with suspended catalyst system without any UV
transparent walls and solar tracking system. The irradiated surface area and
volume of reactor was 0.08 m2 and 5 L respectively. Single baffle reactor
(Reactor 1) was made from an extruded double skinned acrylic panel with
built in flow channels of cross section of 0.4 m 0.1 m. The size of reactor
was 0.4 m 0.2 m 0.1 m. Multiple baffle reactor (Reactor 2) was built of
acrylic in the form of pond divided with baffle plates of about 0.1 m height at
specific intervals. The size of reactor was 0.4 m 0.2 m 0.1 m. Cascade
reactor (Reactor 3) was composed of 6 nos. of acrylic stairs with stair size of
0.16 m 0.08 m 0.1 m (L W H). The wastewater flowed over the steps
before being collected in a tank, from which it was elevated with a pump to
top of the steps for recirculation. Solar pond reactor (Reactor 4) consisted of
shallow pond of size 0.4 m 0.2 m 0.1m open to atmosphere was
fabricated. Evaluation of the solar photocatalytic reactors performance was
carried out by varying the volume of wastewaters in the range of 1-5 L and
the recycle flow rates in the range of 250 750 mL/min. for the degradation
of phenolic wastewaters. The feasibility of enhancement of biodegradability
of phenol, o-cresol, m-cresol and p-cresol wastewater was carried out by

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solar/TiO2/H2O2 system, in a single baffle reactor with volume of wastewater

5 L and recycle flow rate at 500 mL/min.
Sequencing batch reactor of dimensions 20 15 25 cm (L W
H) with a total working volume of 7 L were operated with FILL, REACT,
SETTLE and DRAW periods in the ratio of 1:5:1:1 to constitute a cycle time
of 8 h. Bench-scale optimization studies on phenolic wastewater at influent
concentrations in the range of 100-500 mg/L, aeration time in the range of
5-21 hours and SRT in the range of 10-20 days was studied.
Treatability studies on coupled solar photocatalytic and biological
treatment was studied in semi-continuous flow mode at optimal conditions for
degradation of phenolic wastewaters. The concentration of phenol was varied
in the range of 100-500 mg/L. The wastewaters were transferred to biological
system after solar photocatalytic pretreatment based on evolution of the BOD
/ COD ratio. The design of coupled pilot-plant solar photocatalytic and
biological treatment system was done for treating 1 m3 containing phenol
concentration of 500 mg/L. Total cost of the treatment plant was calculated by
including capital cost and operating cost.

5.3

CONCLUSION
The conclusions drawn from the study are:

Phenolic wastewaters are resistant to biological degradation

with low biodegradability ratio. In this research, the solar
photocatalytic treatment was initiated as a pretreatment
method to increase biodegradability prior to the biological
treatment process.

The control experiments viz. photolysis (without TiO2), dark

adsorption (without solar) and

photocatalysis (solar/TiO2)

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demonstrated that both solar light and a photocatalyst, such as

TiO2 were needed for degradation of phenol. From the
adsorption studies, it was observed that whatever be the pH,
catalyst dosage and phenol concentration the steady state of
adsorption is reached within 30 min.

From the Laboratory-scale feasibility studies on SPCO in

Slurry Catalyst System (SCS), the maximum removal
efficiency was observed at catalyst dosage of 0.25 g/L for
phenol, o-cresol, m-cresol and p-cresol. At pH 6, 7.5, 8 and 6
the maximum removal efficiency of 82 %, 94 %, 90 %, and
98 % was observed for phenol, o-cresol, m-cresol and p-cresol
respectively.

The increase in the pollutant concentration from 10 to

100 mg/L decreases the removal efficiency from 100 to 21 %,
47 %, 37 %, and 7 % for phenol, o-cresol, m-cresol and
p-cresol respectively. In general, the removal efficiency
increased with increase in pollutant concentration up to
50 mg/L and then decreased.

The chloride and sulphate ions give negative impact on the

phenol removal efficiency even at low concentration of
50 mg/L. When compared to aeration during reaction and
without aeration not much difference was observed, it
indicates that oxygen from atmosphere is sufficient for
photocatalytic degradation. It was observed that as the volume
of wastewater was increased, the phenol removal was found to
decrease.

The concentration of phenol, o-cresol, m-cresol and p-cresol

was observed to decrease linearly with increase in contact

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time to solar irradiation. The time taken for 50 % removal

(half life period) was found to be 1.7, 1.1, 1.1 and 1.1 h for
phenol, o-cresol, m-cresol and p-cresol respectively.

The phenol removal efficiency reach its maximum of 95 % at

maximum UV light intensity of 32 W/m2 and the minimum of
59 % at minimum UV light intensity of 20 W/m 2. In general,
average phenol removal efficiency of 73 % at an average UV
light intensity of 23 W/m2 was observed. The phenol removal
efficiency reduced from 95 % to 48 % after 15 trials of
catalyst reuse. 60 % of phenol removal efficiency was
observed after 10 trials of catalyst reuse. Hence, it could be
stated that the catalyst is reusable atleast for 10 times.

From the Laboratory-scale feasibility studies on SPCO in

Fixed Catalyst System (FCS), the phenol removal was found
to be nil for catalyst loading in the range of 0.15 -1 g/L. The
maximum phenol removal of 38 % was observed for the
catalyst loading of 3 g/L. And, the phenol removal efficiency
reduced from 38 % to 15 % after 4 trials of catalyst reuse.

In solar/TiO2 /H2O2 system, the addition of H 2O2 from 0.15

0.3 g/L increases the degradation from 75 to 99 %. When the
H2O2 concentration is higher than 0.3 g/L the degradation rate
decreases. For phenol concentration of 500 mg/L, the phenol
removal efficiency of 45 % and 44 % was observed for entire
amount added in the beginning of reaction and stepwise added
during reaction respectively. It shows that, no substantial
difference between the two cases i.e. one time addition of
H2O2 and stepwise addition of H2O2.

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In solar/TiO2/ H2O2 process, for salt concentration of 50 mg/L,

100 mg/L, 150 mg/L and 200 mg/L the phenol removal was
94 %, 92 %, 90 % and 90 % respectively whereas, in
solar/TiO2 process, the phenol removal was 19 %, 15 %, 12 %
and 12 %

was observed for each corresponding salt

concentration.

In solar/TiO2/H2O2 processes, 97 %, 70 %, 54 %, 47 % and 45

% phenol removal was observed for the initial phenol
concentration of 100, 200, 300, 400 and 500 mg/L
respectively whereas, in solar/TiO2 processes only 54 %, 35
%, 23 %, 22 % and 22 % phenol removal was observed for the
initial phenol concentration of 100, 200, 300, 400 and 500
mg/L respectively.

For an initial concentration of 100 mg/L, the degradation rate

sequences for solar / TiO2 process is o-cresol > m-cresol >
phenol > p-cresol, and for solar/TiO2/H2O2 process, the
sequence is slightly modified to m-cresol > o- cresol > phenol
> p - cresol. When compared to rate of degradation, the solar /
TiO2 / H2O2 process is two to three times faster than the solar /
TiO2 process.

From the bench - scale performance studies on solar

photocatalytic reactors, it was observed that the single baffle
reactor gives the maximum phenol removal efficiency
irrespective of all volume of wastewater. The phenol removal
efficiency increases when the recycle flow rate is increased
from 250 to 500 mL/min and then decreased for the recycle
flow rate of 750 mL/min. The single baffle reactor showed the
maximum phenol removal efficiency with recycle flow rate of
500 mL/min.

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From the biodegradability studies, it was observed that, the

SPCO enhanced the biodegradability up to desired level. For
untreated samples of 100 - 500 mg/L pollutant concentration,
the BOD / COD ratio is 0, while solar photocatalytic treatment
of 2, 2, 3, 4 and 5 hours enhanced the biodegradability values
to 0.53, 0.41, 0.40, 0.44, and 0.40 for phenol concentration of
100, 200, 300, 400 and 500 mg/L respectively. Similarly, the
solar photocatalytic treatment of 1, 1, 2, 3 and 3 hours
enhanced the biodegradability values to 0.57, 0.60, 0.42, 0.48,
and 0.46 for o-cresol concentration of 100, 200, 300, 400 and
500 mg/L respectively. The solar photocatalytic treatment of
1, 2, 3, 5 and 5 hours enhanced the biodegradability values to
0.66, 0.42, 0.42, 0.48, and 0.20 for m-cresol concentration of
100, 200, 300, 400 and 500 mg/L respectively. The solar
photocatalytic treatment of 3, 4, 5, 5 and 5 hours enhanced the
biodegradability values to 0.65, 0.41, 0.31, 0.20, and 0.15 for
p-cresol concentration of 100, 200, 300, 400 and 500 mg/L
respectively.

From the optimization studies of the sequencing batch reactor,

it was observed that inhibitory effect seemed to be more
pronounced with the increase in the phenol concentration from
100 to 500 mg/L. The maximum phenol removal was
observed at SBR cycle time of 8 hours and SRT 10 days.

From the coupled studies, it was observed that, when

500 mg/L concentration of phenol wastewater was subjected
to coupled processes, the solar photocatalytic treatment was
able to remove 44 % of initial phenol concentration in 5 hours
(BOD/COD = 0.40) and the pretreated wastewater was
transferred to the biological treatment, where 93 % removal of

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phenol in 2 hours was achieved. The improvement in the firstorder rate constant (k) value from 0.2 h-1 to 1.2 h-1 in
biological treatment was also observed.

The design of coupled pilot-plant solar photocatalytic and

biological treatment system was done for treating 1 m3
containing phenol concentration of 500 mg/L. The total cost
of wastewater treatment by coupled treatment processes was
estimated to be Rs.526 / m3 of phenolic wastewaters.

Results obtained from this research indicated that the solar

photocatalytic treatment could be a suitable pretreatment method for
enhancing biodegradability of phenolic wastewaters treated in the coupled
solar photocatalytic and biological treatment system. Also, it was observed
that the coupled treatment processes could able to improve the phenol
removal efficiency and reduce the treatment time when compared to the
individual process, which would imply a lower total volume of biological
reactor and lower energy consumption (requirements for mixing and aeration)
to achieve an overall performance to meet the limits of the environmental
legislation.