Desalination and Water Treatment 158 (2019) 87–96

August
www.deswater.com
doi: 10.5004/dwt.2019.24180

Combination of solar advanced oxidation processes and biological

treatment strategy for the decolourization and degradation of pulp and
paper mill wastewater

Ginni Gopalakrishnana, Adishkumar Somanathana,*, Rajesh Banu Jeyakumarb

a
Department of Civil Engineering, University V.O.C College of Engineering, Anna University, Thoothukudi Campus,
Thoothukudi, Tamil Nadu, India, Tel. + 91 9841339016; Fax: 0462 2552877; email: [email protected] (A. Somanathan),
Tel. + 91 9942491180; email: [email protected] (G. Gopalakrishnan)
b
Department of Civil Engineering, Regional centre of Anna University, Tirunelveli, Tamil Nadu, India, Tel. + 91 9444215544;
email: [email protected]

Received 5 September 2018; Accepted 27 March 2019

abstract
This study is focused on the investigation of seven treatment strategies and the percentage reduction
on COD and colour was evaluated and total time required for different treatment strategies were
calculated. The results revealed that the COD and colour removal of 97% and 92%, respectively, was
attained at 180 min of treatment for the coupled SPF-biological process, 97% and 90% of COD and
colour removal was attained at 195 min of treatment for the coupled SPC-biological process whereas
98% and 95% of COD and colour removal at 95 min of treatment for the coupling of combined
SPF-PC-biological process confirming the efficiency of the coupled process with a relatively shorter
reaction time compared with the other processes. The values of the first order kinetics for the
combined SPF-PC-biological process were 0.03 min–1 which is eight times greater than the biological
process and 1.4 and 1.87 times faster than the coupled SPF-biological and SPC-biological process,
respectively. The economic analysis of various AOPs and the relative cost of AOP–biological pro-
cesses were discussed and the coupling of combined SPF-PC-biological process was found to be a
technically and economically effective in treatment of pulp and paper mill wastewater to meet the
effluent discharge standard.
Keywords: Advanced oxidation processes; Biodegradability; Coupled AOP and biological process;
Economic assessment; Pulp and paper mill wastewater

1. Introduction environments [3]. The conventional biological treatments

such as aerated lagoon or activated sludge are used for
The pulp and paper industry is a very water-intensive
the treatment of pulp and paper mill wastewater. But their
industry and consumes about 100–250 m3 of freshwater per
applicability is limited by a number of problems due to
ton of paper produced [1]. About 175 m3 of wastewater is
their incomplete degradation which generates potentially
generated per ton of paper produced. The main source of
hazardous intermediates because the biologically treated
wastewater comes from the pulping, bleaching and paper
wastewater does not eradicate the complex organics and
making processes [2]. Wastewater from pulp and paper indus­
presence of considerable amounts of recalcitrant organics
tries contains high concentrations of organic matter, colour,
after treatment contribute colour and substantial amount
phenolic compounds of high molecular weight, and other
of COD [4]. Some economic and environmental friendly
toxic substances that can cause significant damage to aquatic
alternative to conventional methods have been developed
known as advanced oxidation process [5].
* Corresponding author.

1944-3994/1944-3986 © 2019 Desalination Publications. All rights reserved.

88 G. Gopalakrishnan et al. / Desalination and Water Treatment 158 (2019) 87–96

Advanced oxidation processes have recently emerged as The raw wastewaters from various unit operations namely
a suitable technique to treat wastewaters capable of generat- pulping, pulp washing, bleaching and paper making pro-
ing highly oxidizing radical species such as OH• oxidizing cess are mixed together and the amount of wastewater
most recalcitrant organic compounds and completely discharged from the mill is 15,000 m3/d. The samples were
mineralize them into CO2, H2O and inorganic ions. Among collected from the collection tank without modifications.
AOPs, solar photo-Fenton (solar/Fe2+/H2O2) and solar The samples were transported to the laboratory in plastic
photocatalysis (solar/TiO2/H2O2) have been considered to cans and stored at 4°C. The physicochemical character-
be the most promising tools in context to pollutants abate- istics of the wastewater were analyzed as per standard
ment [6]. The application of homogeneous Fenton’s reagent methods [13] and it was determined as pH = 6.99 ± 0.1,
is limited by the narrow pH. Solar photocatalytic oxidation colour (at 465 nm) = 0.848 ± 0.100, COD = 1,800 ± 400 mg/L,
using TiO2 semiconductor is very efficient in wastewater BOD5 = 400 ± 50 mg/L and BOD5/COD = 0.22 ± 0.05.
treatment because of its high photocatalytic efficiency and The quantification of BOD5/COD ratio was done to deter-
chemical stability [7]. The disadvantage of this treatment mine biodegradation potential and the value lower than
process is that the conventional TiO2 powder has low con- 0.4 being considered as indicative of the presence of toxic
version efficiency. The combining of solar photo-Fenton and or recalcitrant contaminants [14].
solar photocatalysis processes (solar/Fe2+/TiO2/H2O2) is an
attractive option which leads to maximum efficiency due to
utilizing both the UV and visible region from solar radia- 2.2. Chemical reagents
tion. The use of sunlight as source of irradiation to perform The experiments were performed using ferrous sulphate
AOPs reduces operating costs and makes it more reason- heptahydrate (FeSO4 7H2O) reagent-grade hydrogen per-
able for commercial use as a water treatment technology [8]. oxide (H2O2) (30%, w/w) to obtain hydroxyl radical OH•.
Another attractive way of reducing costs is the coupling of Sulphuric acid (H2SO4) and sodium hydroxide (NaOH)
AOPs with biological treatment in a combined technology. were used for the pH adjustment. The photocatalyst
The combination of AOPs with an inexpensive bio­logical employed was commercial TiO2 (P-25), supplied by Degussa
treatment, capable of reducing from the outset the biode- (Germany). According to the manufacturer’s specifications,
gradable fraction, turns the overall process less expensive P-25 has an elementary particle size of 30 nm, Brunauer,
and, therefore, more economically attractive [9]. Sequencing Emmett and Teller specific surface area of 50 m2/g and crys-
batch biological reactor (SBR) is a wastewater treatment pro- talline mode comprising 80% anatase and 20% rutile. Sodium
cess based on the principles of the activated sludge process thiosulphate (Na2S2O3), potassium dichromate (K2Cr2O7),
is typically used in combined systems due to its simplicity, mercuric sulphate (HgSO4) and ferrous ammonium sulphate
flexibility of operation, small floor space requirements and (Fe(NH4)2(SO4)2.6H2O) were used for COD analysis. Sodium
good removal efficiency [10]. The SBR operation treatment sulphite (Na2SO3) was used to quench the reaction. All the
cycle can be divided into the following five stages: filling, reagents used in this experiment were of analytical grade and
reaction, settling, decantation, and idle. All these stages used without further purification.
occur in a single reactor. In addition, the hydraulic retention
time (HRT) can be adjusted by varying the decanted volumes
after a settling period [11]. There are several advantages of 2.3. Experimental procedure
SBR over other reactors used in wastewater treatment and
2.3.1. AOP pretreatment
also the initial cost of this method is lesser compared with
other treatment techniques [12]. All photocatalytic experiments were carried out at
The treatment of the wastewater by solar photo-Fenton, Anna University Campus, Tirunelveli, India (8°44′N 77°44′E).
solar photocatalysis and combined solar photo-Fenton-­ The experiments were carried out in a solar photocatalytic
photo­catalysis was optimized as previously reported. The plug flow baffle reactor. Experiments were conducted under
pretreatment of the wastewater was conducted under opti- solar illumination on clear sky days from January to April
mum conditions obtained from the previous experiments with the solar light intensity 103 ± 2 W/m2. Initially, the pH
and the pretreated wastewater was subjected to biological was adjusted using either sulphuric acid or sodium hydroxide
treatment by SBR to make the wastewater consistent with at the beginning of the reaction. Then the required amount
the standard discharge limits. The objective of this study was of ferrous sulphate and/or TiO2 was added to the wastewater
to investigate the effectiveness of the coupled solar photo-­ and mixed well to enhance the homogeneity of the waste-
Fenton followed by biological process (SPF-SBR), coupled water during the reaction. The samples were taken from
solar photocatalysis followed by biological process (SPC-SBR) the solar photocatalytic plug flow baffle reactor at specific
and the combined solar photo-Fenton-­ photocatalysis fol- time intervals for COD and colour analysis. To the collected
lowed by biological process (SPF-PC-SBR) for the treatment samples, quenching was done by adding sodium sulph-
of pulp and paper mill wastewater. ite solution (2 mL) and then samples were filtered through
filter paper (0.42 mm Millipore membrane) to remove the
catalyst. The COD was determined using the dichromate
2. Materials and methods closed reflux method according to the standard methods
[13]. Biochemical oxygen demand (BOD5) was determined at
2.1. Source and characterization of the wastewater
20°C using the standard dilution technique according to the
The wastewater samples used were obtained from the standard methods [13]. All the experiments were performed
pulp and paper mill located near Erode, Tamil Nadu, India. in triplicate.
 G. Gopalakrishnan et al. / Desalination and Water Treatment 158 (2019) 87–96 89

2.3.2. Sequencing batch biological reactor treatment and reuse of processed water. As per the Minimum National
Standards (MINAS) standards and TNPCB standards,
After pretreatment by AOP, the effluent was collected for
the discharge limits of pulp and paper wastewater is
subsequent biological treatment. The biological treatment
COD = 100 mg/L, BOD5 = 30 mg/L and TSS = 20 mg/L.
was carried out in SBR using a reactor made of plexiglass
with a total volume of 7 L with operating volume of 5 L.
The SBR was equipped with an air pump and air diffuser to 3. Results and discussion
keep dissolved oxygen above 3 mg/L. In the case of biolog-
3.1. Solar photo-Fenton process
ical treatment alone, the SBR was operated with the HRT of
24 h for each sequential phase of 0.5 h feeding, 22 h aera- The experiment was carried out previously by varying
tion, 1 h for settle phase and 0.5 h for removal phase with pH in the range of 2–6 and Fe2+ from 0 to 0.30 g/L and H2O2
sludge retention time of 15 d. The SVI value was in the range from 0 to 5 mL/L. The highest COD and colour removal of
of 80–90 mL/g, indicating good sludge settleability. 70% and 76%, respectively, was obtained at 60 min of treat-
ment process under the optimum conditions viz. pH – 3,
Fe2+ – 0.24 g/L and H2O2 – 4 mL/L. Therefore, the optimized
2.3.3. Combination of AOPs with SBR treatments
values obtained from previous stages were used to gain the
For the coupled AOP-biological process, HRT 3.75 h was optimal contact time to meet the target COD. The influence
used and it was divided into five phases: filling (0.25 h), of contact time on COD removal, colour removal, BOD5
aeration (2 h), settling (1 h), decant (0.25 h) and idle (0.25 h). removal and BOD5/COD ratio is shown in Fig. 2. The find-
Pretreated wastewater was used to feed the SBR after pH ings illustrated that an increase in contact time increased the
adjustment to 7.0. The MLSS concentration after inocu- removal efficiency and allowed the utilization of more solar
lation in the reactor was 4,000 ± 1,000 mg/L. Aeration and energy to produce hydroxyl radicals from H2O2. At 15 min
agitation of the reactor was ceased during the settle phase of contact time, the COD and colour removal was 41% and
and sludge was allowed to settle under quiescent condi- 32%, respectively, and the removal efficiency of COD and
tion. The supernatant collected after settling was filtered colour increased to 97% and 98% when the contact time
through 0.45 µm filter for measurement of COD and BOD5. was increased to 150 min which met the discharge limits as
A schematic layout of the combined AOP-SBR process is per the MINAS and TNPCB standards. Further increasing
shown in Fig. 1. the contact time to 165 min, the complete COD and colour
removal efficiencies (100%) were attained [15,16].
2.4. Treatments The biodegradability of raw wastewater was found to
be 0.22 and this indicates the presence of non-biodegradable
The pulp and paper mill wastewater was treated by organic compounds. After the treatment by SPF, the biode-
seven treatment strategies such as (i) solar photo-Fenton pro- gradability ratio increased and reached 0.4 at 60 min of solar
cess (SPF); (ii) solar photocatalytic process (SPC); (iii) SBR irradiation which turned the wastewater biodegradable
treatment; (iv) combined SPF-PC process (SPF-PC); (v) SPF as reported before [17]. At this point, the wastewater was
followed by biological process (SPF-SBR); (vi) SPC followed transferred to SBR for the biological degradation.
by biological process (SPC-SBR); (vii) SPF-PC followed by
biological process (SPF-PC-SBR). In order to meet the strin-
3.2. Solar photocatalytic process
gent regulations, the Tamil Nadu Pollution Control Board
(TNPCB) has directed the industries to implement zero The experiments were carried out previously by vary-
discharge facilities and the high consumption of water by ing pH in the range of 2 to 10 and Fe2+ from 0 to 0.30 g/L
pulp and paper industries has necessitated the recycling and H2O2 from 0 to 5 mL/L. The highest COD and colour

Fig. 1. Schematic layout of the combined AOP-SBR process.

90 G. Gopalakrishnan et al. / Desalination and Water Treatment 158 (2019) 87–96

Fig. 2. Experimental steps for designing wastewater treatment by solar photo-Fenton process (pH = 3, Fe2+ = 0.24 g/L, H2O2 = 4 mL/L,
solar intensity = 103 W/m2).

removal of 69% and 78%, respectively, was obtained at removal efficiency increased to 95% and 98%, respectively.
60 min of treatment process under the optimum conditions The discharge standard was achieved at 180 min of contact
viz. pH – 6, TiO2 – 0.25 g/L, H2O2 – 3 mL/L. The effect of time while the complete COD and colour removal efficiencies
contact time was determined with the optimum conditions were attained at 195 min of contact time. In this process, the
previously determined to meet the target COD. The influ- biodegradability limit was attained at contact time of 75 min.
ence of contact time between COD removal, colour removal, Therefore, this time was chosen as sufficient for the photo-
BOD5 removal and BOD5/COD ratio is shown in Fig. 3. It chemical pre-biological step.
could be observed that longer the contact time greater the Even though AOPs are highly efficient for the treatment
COD and colour removal. For 60 min of contact time, the of highly polluted wastewater; their operation is still quite
COD and colour removal were 65% and 82%, respectively. expensive. The effective degradation of wastewater by AOP
Whereas for 165 min of contact time, the COD and colour alone varied in the consumption of H2O2. It was observed

Fig. 3. Experimental steps for designing wastewater treatment by solar photocatalytic process (pH = 6, TiO2 = 0.25 g/L, H2O2 = 3.00 mL/L,
solar intensity = 103 W/m2).
 G. Gopalakrishnan et al. / Desalination and Water Treatment 158 (2019) 87–96 91

that the oxidation of wastewater by single AOP is an uneco- the 24 h cycle. Colour removal efficiency by the biological
nomical technology. Therefore, the advantage of coupling process alone was low because colour results from the
AOP with biological process was to reduce the treatment presence of the lignin or polymerized tannins, compounds
costs, particularly the hydrogen peroxide concentration with high molecular weight, which are nontoxic but poorly
used in the AOP. It is noteworthy that during the AOP biodegradable [21].
pretreatment process, the reaction can be carried out at a low
ferrous iron dosage resulting in the negligible amount of 3.4. Combined s+olar photo-Fenton-photocatalytic process
sludge generation. This can solve the problem of sludge dis- (SPF-PC)
posal, thereby adding to the cost-effectiveness of the process.
The experiments were carried out previously by varying
pH in the range of 3–11 and Fe2+ from 0 to 0.30 g/L, TiO2
3.3. Treatment of pulp and paper mill wastewater by from 0 to 0.25 g/L and H2O2 from 0 to 5 mL/L. The highest
biological process (SBR) COD and colour removal of 70% and 76%, respectively, was
obtained at 60 min of treatment process under the optimum
The SBR was operated for the treatment of pulp and
conditions viz. pH – 7, Fe2+ – 0.10 g/L, TiO2 – 0.13 g/L and
paper mill wastewater under optimum conditions of the pro-
H2O2 – 1.80 mL/L determined previously [22]. The opti-
cess variables. The removal performances of COD and colour
mized values obtained from previous stages were used to
were examined as depicted in Fig. 4. The SBR was operated
gain the optimal contact time to meet the target COD. The
with the influent COD concentration of 1,800 mg/L. The
influence of contact time between COD removal, colour
effluent COD concentration after SBR treatment was found
removal, BOD5 removal and BOD5/COD ratio is shown
to be 260 mg/L at 6 h of reaction time. It was observed that
in Fig. 5. It could be observed that the increase in contact
the COD removal percentage was increased from 2 to 6 h and
time increased the COD and colour removal. For 20 min
afterwards with the gradual increase in COD removals up
of contact time, the COD and colour removal was 72% and
to 12 h. Increasing HRT from 12 to 24 h did not significantly
77%, respectively. Whereas for 75 min of contact time, the
improve the SBR performance. This indicates that most of
COD and colour removal efficiency increased to 97% and
the substrate degradation occurred during the first 6 h and
96%, respectively, as per the discharge standard. The com-
a smaller portion was degraded in rest of the retention time.
plete COD and colour removal efficiencies were attained at
According to Metcalf & Eddy [18], the biodegradable
90 min of contact time.
fraction of the COD can be divided into a slowly biode-
It was found that the initial biodegradability ratio of
gradable fraction and a readily biodegradable fraction.
pulp and paper mill wastewater was increased steadily after
This is because in SBR system, only biodegradable organic
pretreated by SPF-PC process. In this process, the biodegrad-
compounds were removed thereby the resulting wastewater
ability limit was attained at contact time of 20 min. Therefore,
contains most of the non-biodegradable organic compounds
this time was chosen as sufficient for the photochemical
[19]. The fast biodegradable organic compounds include
pre-biological step.
short chain volatile organic acids and more complex organic
acids. Thus the findings from SBR suggest that the percent-
3.5. Coupling of solar photo-Fenton followed by biological
age removal of readily biodegradable organic compounds
process (SPF-SBR)
was attained at HRT as 6 h [20]. The COD removal efficiency
was observed to be 85% while the removal efficiency of colour The initial effluent concentration of COD of pulp and
was found to be 57%. However, it is impossible to extend the paper mill wastewater was 1,800 mg/L and BOD 396 mg/L.
aeration time limitless due to the increase of operating cost. After pretreatment by SPF process, the effluent concentra-
Measurement of COD showed that the 12 h aeration time tion of COD and BOD value reduced to 500 and 200 mg/L,
was able to achieve similar removal efficiencies as that of respectively. The pretreated wastewater was then trans-
ferred to SBR for biological degradation with the BOD5/
COD ratio as 0.4. The degradation of wastewater in a
100 450
coupled SPF followed by biological process is given in Fig. 6.
90 400 The influence of the SPF-SBR process was undertaken and
80
compared with the biological process. It was observed that
350
the removal efficiency of COD, BOD and colour increased
COD & colour removal (%)

70
300 with the increase with the contact time. The overall organic
BOD removal (mg/L)

60 removal efficiency confirmed 97% COD, 92% BOD and

250
50 COD (mg/L) 92% of colour removal by the coupled SPF-SBR process at
colour (%)
BOD (mg/L) 200 180 min of treatment process (phototreatment time = 60 min,
40 HRT in SBR = 120 min). The output of the result detailed that
150
30 the efficiency of the coupled SPF-SBR process was higher
100 relative to the biological process alone since in the coupled
20
process, a significant portion of recalcitrant organic com-
50
10 pounds is degraded chemically during pretreatment which
0 0 converts the non-biodegradable compounds into more
0 2 4 6 8 10 12 14 16 18 20 22 24
Time (h)
easily biodegradable organic compounds and is made bio-
logically available to the following biological treatment [23].
Fig. 4. Degradation of wastewater in SBR. The study by Elmolla and Chaudhuri [24] showed that the
92 G. Gopalakrishnan et al. / Desalination and Water Treatment 158 (2019) 87–96

Fig. 5. Experimental steps for designing wastewater treatment by combined solar photo-Fenton and solar photocatalytic process
(pH = 7, Fe2+ = 0.10 g/L, TiO2 = 0.13 g/L, H2O2 = 1.80 mL/L, solar intensity = 103 W/m2).

Fig. 6. Degradation of wastewater in a combined solar photo-Fenton and SBR.

combined Fenton-SBR process achieved the COD removal of the enhancement in biodegradability. It was observed that
89% with the Fenton reaction of 120 min and SBR with the the biodegradability ratio of pulp and paper mill wastewa-
HRT of 12 h. Vidal et al. [23] treated the tannery waste­water ter was increased steadily when pretreated by SPC process
by sequential AOP-biological treatment which increased and when it reached 0.4, the pretreatment was stopped at
the overall COD removal up to 96%, compared with 60% this oxidation time corresponding to the BOD5/COD ratio.
without pretreatment. After pretreatment by SPC process, the effluent concen-
tration of COD was decreased from 1,800 to 545 mg/L and
3.6. Coupling of solar photocatalysis followed by biological with this concentration of COD; the pretreated wastewater
was subjected to biological degradation. The degradation
process (SPC-SBR)
of wastewater in a coupled solar photocatalysis followed
The pretreatment of wastewater was carried out with by biological process is given in Fig. 7. The overall organic
the optimum conditions obtained previously to determine removal efficiency confirmed 97% COD, 92% BOD and
 G. Gopalakrishnan et al. / Desalination and Water Treatment 158 (2019) 87–96 93

Fig. 7. Degradation of wastewater in a combined solar photocatalytic and SBR.

90% of colour removal by the coupled SPC-SBR process at as high as reported by other researchers working on coupled
195 min of treatment process (phototreatment time = 75 min, AOP-biological process. Li et al. [27] evaluated the perfor-
HRT in SBR = 120 min). The efficiency of this coupled pro- mance of coupled AOP-biological system for the degrada-
cess was observed to be greater than the biological process tion of Cibacron Yellow LS-R commercial dye. The coupled
alone with the three fold reduction in treatment time. In a system completed the dye degradation in 34 h, reaching a
literature, a study reported by Zapata et al. [25], the effi- mineralization level of 70%, measured as COD. Guzmán
ciency of the combined photo-Fenton/bio system in terms et al. [28] studied the degradation of citrus wastewater by
of mineralization was found to be 94%, of which 35.5% the combined solar photo-Fenton and sequential batch reac-
corresponds to the AOP and 58.5% to the aerobic biological tor. The results showed degradation yields up to 93% of
treatment. the initial DOC removal without producing undesired side
effects, using an HRT of 1.59 d.
3.7. Coupling of combined solar photo-Fenton and photocatalytic
with biological process (SPF-PC-SBR) 3.8. Kinetics
The pretreatment of wastewater was carried out with the The kinetics for the treatment of pulp and paper mill
optimum conditions obtained previously to determine the wastewater was studied to evaluate the treatment method.
enhancement in biodegradability. The biodegradability ratio The kinetic rate constant for the AOP and SBR processes was
of pulp and paper mill wastewater was increased steadily estimated by drawing a plot of ln (C/C0) vs. time under opti-
when pretreated by SPF-PC process. It was observed that mum conditions. The straight line obtained indicates that
the concentration of COD of the wastewater decreased from the reaction followed the pseudo-first order reaction with
1,800 to 600 mg/L after pretreatment by SPF-PC process and high value of coefficient R2. The higher the degradation rate
with this COD concentration, the pretreated wastewater constant, the higher or faster is the rate of degradation. The
was subjected to biological degradation. The degradation reaction rate constant and half life time are given in Table 1.
of wastewater in coupling of combined solar photo-­Fenton- The SBR process followed the pseudo-first order kinetics
photocatalytic followed by SBR is given in Fig. 8. The degra- and the biokinetic rate constant was found to be 0.0035 min–1.
dation of wastewater increased with the increase in contact This was compared with the biokinetics of coupled AOP-SBR
time during the biological oxidation. The results obtained process. It was observed that after pretreatment by SPF pro-
showed that the highest removal efficiency for the coupled cess, SPC process and combined SPF-PC process, the order
system overcomes the limitations in the degradation effi- of kinetic rate constant was found to be combined SPF-PC
ciencies obtained during the individual implementation of followed by SBR (0.037 min–1) > solar photo-Fenton followed
combined SPF-PC pretreatment and biological activity [26]. by SBR (0.02 min–1) > solar photocatalysis followed by SBR
The output of the result detailed that the overall organic (0.016 min–1) > SBR (0.0035 min–1).
removal efficiency confirmed 98% COD, 92% BOD and 95% The half-life time of various treatment strategies was
of colour removal at 95 min of treatment process (phototreat- calculated. The half-life time is the time required to decrease the
ment time = 20 min, HRT in SBR = 75 min). These results are concentration of the reactant to half of the initial value [29].
94 G. Gopalakrishnan et al. / Desalination and Water Treatment 158 (2019) 87–96

Fig. 8. Degradation of wastewater in a combined solar photo-Fenton and photocatalytic with SBR.

Table 1
Reaction rate constant and half life time of various treatment strategies

Initial COD Final COD Kinetic constants Half life time

S. no Treatment strategies (mg/L) (mg/L) (min–1) (t1/2) min
1 Solar photo-Fenton 1,800 45 0.0199 34.82
2 Solar photocatalytic 1,800 45 0.0159 43.58
3 Combined solar photo-Fenton and
photocatalytic 1,800 45 0.0537 12.9
Pretreatment Biological Pretreatment Biological
4 Coupled solar photo-Fenton and biological 1,800 45 0.018 0.021 38.5 33
5 Coupled solar photocatalytic and biological 1,800 45 0.013 0.016 53.3 43.3
6 Coupled solar photo-Fenton and Solar 1,800 45 0.04 0.03 17.32 23.1
photocatalytic and biological
7 Biological process 1,800 150 0.0035 198

The degradation half-life times (t1/2) are calculated by the reaction is more suitable for the combined SPF-PC than the
equation as follows: other two processes. Also, the synergetic effect between the
SPF and SPC process was quantified by the rate constants and
0.693 it was found to be 1.50. Thus the outcome of the experimental
t1/ 2 =
k results revealed that the combination of SPF-PC process was
found to be more efficient than the individual process with
It was observed from the table that the half-life time of
less consumption of chemical reagents and short reaction
the combined SPF-PC process was less among AOPs and also
time. Therefore, a feasible option is the partial oxidation of
among the coupled AOP-biological processes, half-life time
recalcitrant pollutants in AOPs and the subsequent treat-
was less for the coupling of combined SPF-PC with biologi-
ment in a biological process. This exploits the advantages
cal process. The higher the kinetic rate constant, lesser is the
of both processes by choosing the reaction time as short as
half-life time.
possible to achieve partial oxidation and to guarantee the
Moreover, a significant enhancement of the degrada-
economic feasibility of the AOP pretreatment [30].
tion rate was observed during application of the combined
SPF-PC process. The reaction rate for the combined SPF-PC
3.9. Comparative study of economic assessment
process was found to be 2.69 times faster than SPF pro-
cess and 3.37 times faster than SPC process. The values of In a view of a wastewater treatment system, it is necessary
correlation coefficients indicate that the pseudo-first order to assess the economic feasibility of the various treatment
 G. Gopalakrishnan et al. / Desalination and Water Treatment 158 (2019) 87–96 95

strategies. The economic assessment was evaluated by con- to be more cost-effective because shorter HRT decreases the
sidering the following parameters: reagents consumption installation cost. Thus the retention time was reduced to more
based on solar irradiation, labour and investment costs. The than half of that needed for the biological treatment alone
radiation energy and the chemical reagent costs are the main [31]. Thus the coupling of combined SPF-PC with biological
factors that influence the treatment process. In this study, process resulted in reduction of total costs avoiding unnec-
only the chemical reagents were considered for the cost esti- essary expenditure on chemicals which represents the most
mation. The use of abundant solar light reduced the costs of economically feasible process reducing the potential health
the AOPs. The cost estimation was done for a flow rate of and environmental risks by providing treated wastewater for
15,000 m3/d. The estimated annual cost of treatment for the reuse purposes.
individual AOP and the coupled AOP and biological process
are depicted in Fig. 9. The cost of treatment of wastewater
was found to be Rs. 1,887/m3, Rs. 1,652/m3 and Rs. 990/m3 4. Conclusion
for the SPF, SPC and SPF-PC process, respectively. The cost The pretreatment by solar photo-Fenton, solar pho-
of treatment of wastewater by the coupled AOP-biological tocatalysis and combined solar photo-Fenton and photo­
process was estimated and it was determined as Rs. 926/m3, catalytic process showed to be successful approach for the
Rs. 707/m3 and Rs. 423/m3 for the SPF-SBR, SPC-SBR and biological treatment of pulp and paper mill wastewater. The
SPF-PC-SBR process, respectively. It was observed that the pretreatment by solar photo-Fenton, solar photocatalysis and
calculated treatment cost in the combined SPF-PC process combined solar photo-Fenton and photocatalytic process
was lower than the individual process due to highly reduced enhanced the biodegradability from 0.22 to 0.4 in 60, 75
reaction time. The results revealed that the treatment costs of and 20 min of phototreatment, respectively. Thus the pho-
combined SPF-PC process was 1.14 and 1.90 times less than totreatment processes led to the COD removal resulting in a
that of SPF and SPC process. Compared with the treatment biodegradability enhancement being possible to couple with
costs of AOPs alone, the treatment costs of coupling of com- a further biological treatment, achieving a final wastewater
bined SPF-PC-biological process was 2.34 times less than that quality in agreement with discharge limits into receiving
of combined SPF-PC process. water bodies. The degradation of pulp and paper mill waste-
The main advantage of the application of coupled SPF- water by various treatment strategies accorded well with
biological process was the efficient COD and colour removal the pseudo-first order reaction kinetics. After pretreatment
with the possible reduction in treatment time without by SPF process, SPC process and combined SPF-PC pro-
affecting the efficiency of the SPF process with less reagent cess, the biokinetic rate constant was found to be more for
consumption and consequently cost reduction [21]. Thus the combined SPF-PC-biological process and gave better
from the above discussions, the combined SPF-PC pro- results relative to the other treatment strategies and was
cess showed better results operating at an optimal pH of 7 considered economically feasible, able to achieve up to 98%
thereby it overcomes the drawbacks of the individual process COD and 95% colour removal with a total cost of 4.5 US$/
because no pH adjustment is necessary for the degradation m3 of treated water. Thus the economic evaluation showed a
of pulp and paper mill wastewater. Biological treatment as a marked increase in removal efficiency resulting in reduction
single process could achieve an acceptable reduction in 12 h in reagent costs and reaction time.
whereas there was a significant reduction in detention time
in the coupled AOP-biological process which is considered
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