CHAPTER-II

Literature Review

2.1 Overview

Currently, contamination of water is one of the major problems of the entire globe, due to the
improper discharge of used water of the industries into the environment, high utilization of
chemical fertilizers in agricultural fields, construction of roads, buildings, etc. Hence the
wastewater is needed to be treated well before it is discharged into the environment or used
for other purposes (Fallis, 2007). In this review, advanced treatment methods of wastewater
such as nano photocatalyst application, ceramic membrane filtration, ceramic membrane
filtration integrated with nanophotocatalysis, chemical and biological methods including
application of biofilms, are discussed in detail.

2.2. Advanced Oxidation Process for Wastewater Treatment

Both organic and inorganic pollutants present in the wastewater are removed by a set of
chemical treatment methods. Among various chemical processes used wastewater treatment,
the oxidation process is broadly employed and is known as the advanced oxidation process
(AOP). In this process, for water purification, an adequate amount of hydroxyl radicals (OH•)
are generated and this notion was later expanded to sulfate radicals (SO4 •−) oxidative
processes.

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Table 2.1. Application of advanced oxidation processes (AOPs) for the treatment of various
textile effluents containing dyes
Method Wastewater Results Ref.
Heterogeneous Remazol Brilliant More than 90% of COD removal was (GAR
Photocatalysis Blue R, Red achieved, and the H2O2 added was CIA
Procion, Yellow completely absorbed. At 430 nm, 100 and et al.,
Procion (EFA, 67.36% of EFC and EFB effluents were 2007)
EFB, and EFC degraded respectively.
textile industry
effluents)
Chemical Color and COD AOP results in 60% of COD and 50% of (Azba
treatment removal from color removal, while 96% of color and 99% r et
techniques acetate and of COD removal was achieved by al.,
(Fe2+/H2O2, polyester fiber integrating the AOP with the O3/H2O2/UV 2004)
H2O2/UV, O3, dyeing effluent conventional method.
etc) and advanced
oxidation
processes
Advanced Cotton-textile At 60 mg catalyst loading, 85.5% (Soar
oxidation dyeing mineralization, and 98.5% decolorization es et
processes (AOPs) wastewater was achieved in the solar-photo-Fenton al.,
process. While, by integrating the biological 2014)
process with solar-photo-Fenton reaction,
0.5 kJUV L−1 of photo treatment energy and
7.5 mM of H2O2 is required to attain the
COD below 250 mg O2 L-1
Advanced Textile dye bath On the application of H2O2/UV on (Muh
oxidation effluent biotreated dye bath effluent, 98% of amma
processes decolorization was achieved. Application of d et
(H2O2/UV, UV, AOPs following the biotreatment has al.,
O3) surpassed the biodegradability. 2008)

13
Apart from the degradation of organic and inorganic pollutants, AOPs have also been studied
for pathogen and pathogenic indicators inactivation. The recalcitrant organic pollutants
present in the wastewater can be swiftly degraded by the strong oxidants and hence AOPs
have been considered as the best technologies for wastewater treatment (Deng and Zhao,
2015). Some of the recent studies on textile dye wastewater treatment using AOPs are
discussed in table 2.1. Guimarães et al., 2012 studied the Reactive Blue 19 (RB-19) dye
degradation by employing several AOPs such as the photo-Fenton process, H2O2/Fe2+,
H2O2/UV, peroxidation, UV, etc. At 500 mg L-1 H2O2 and 3h reaction time, 91% of dye was
degraded by the H2O2/UV process. Within a very short span of the reaction, more than 98% of
color and 36.8% of dissolved organic carbon were removed by Fenton reagent and 99.4% of
color and 94.5% of dissolved organic carbon were removed through the photo-Fenton
process. Because of this efficiency, this method is considered to be an efficient method by
many researchers. A reduction of 93% BOD, 80% COD, 85% color, and 88% of dissolved
organic carbon was observed when the photo-Fenton process was integrated with the
biological system.

2.3 Employment of Nano photocatalyst in wastewater treatment

The advanced oxidation processes (AOPs) have secured an unprecedented acceptance

regarding the progress of wastewater treatment methods for two decades. At piolt scale,
recalcitrant organic contaminants are efficiently degraded by employing few technologies,
such as photocatalytic oxidation, ozonation, cavitation, and Fenton process. In the wastewater
treatment domain, many researchers have worked on heterogeneous and homogenous AOPs
in advance..Several oxidants like O3, H2O2, etc. and catalysts including ZnO, TiO2 and
UV/visible light are engaged for AOPs instigation. AOPs generate •OH radicals during the
stimulation and reciprocate with organic compounds in the dissolved O2 vicinity. The
enormous utilization of organic dyes by paper, printing, textile dyeing and various other
industries is leading to severe environmental pollution. The existence of dyestuff in water will
obstruct the reflection and absorption of the sunlight and it leads to noxious concentration
accumulation which effects the water bodies. By using dynamic AOPs, complete breakdown
of organic colorants can be attained.

14
Profitable mineralization of dye pollutants in aqueous media using various AOPs was
explained by several researchers. The photocatalytic AOP could commence the intricate chain
reactions and there is also a chance of generation of uncolored organic intermediates and the
generated intermediates sometimes become poisonous. According to the literature available,
few studies have disclosed that the microsize catalysts are utilized in various AOPs for the
organic composites mineralization, but utilization of nanomaterials in AOPs for the
wastewater treatment has not been reported (Chang et al., 2009; Geng et al., 2009). Some of
the semiconductors like TiO2, CdS, ZnO, WO3 that have been used as photocatalysts are
reported by Elamin and Elsanousi, 2013. Among the photocatalytic materials studied, ZnO is
considered as one of the finest materials for the efficient breakdown of organic contaminants.
Various studies have also revealed that ZnO is highly reactive photochemically, economical,
and non-toxic in terms of organic contaminants breakdown when compared to TiO2 (Ali et al.,
2010; Danwittayakul et al., 2015, 2013a; Huang et al., 2012; Pardeshi and Patil, 2009; Strunk
et al., 2009). It would be advantageous if ZnO assimilates visible light apart from UV light
and it will benefit in the enhancement of photocatalytic efficiency. Moreover, it is possible to
absorb the visible light by bifurcating the ZnO bandgap into various sub gaps, and the
bifurcation of ZnO can be attained by nitrogen doping (Elamin and Elsanousi, 2013).
Different researchers have reported, that since two decades the organic pollutants
mineralization was substantially ameliorated by using nanocrystalline TiO2 and ZnO as
photocatalysts (Min et al., 2007; Moon et al., 2003; F. Peng et al., 2006; Pouretedal et al.,
2009; Suárez-Parra et al., 2003; Venkatachalam et al., 2007; Wang et al., 2007; Yu et al.,
2005).

.OH + h+ → .OH (2.1)

H2O + h+ → .OH + H+ (2.2)

Around 70-80% of the literature in the wastewater treatment by employing photocatalysis and
ZnO/TiO2 as a photocatalyst is available and researchers have examined the usage of doped
TiO2 for the contaminant braekdown. Because of the wide bandgap (3.2eV), TiO2
photocatalyst is called as semiconductor and parallels to radiation in the close UV range it is
advantageous correleated to alternative photocatalysts. A set of electrons and holes are
generated in the conduction and valence band upon excitation of TiO2/ZnO particles to UV
light irradiation. The charged species could relocate to the surface of the particle or they can

15
combine with the dissolute heat from the absorbed energy and the holes to form hydroxyl
radicals (OH·) that reacts with OH− group and adsorb H2O molecules. To initiate with the
photocatalytic reaction wherein the organic pollutants mineralization in wastewater, the
photocatalyst and light source are absolutely needed. Contemporary research has been
centered on the viable utilization of visible light/sunlight for initiating the photocatalytic
reaction and this will save a lot of resources, energy, and also minimize the operating costs.
Some of the recent studies on textile dye wastewater treatment using photocatalysis are
discussed below in Table 2.2.

Table 2.2. Application of UV-visible induced nanomaterials as photocatalysts for the

mineralization of various organic contaminants in aqueous solutions
Method Wastewater Results Ref.
Photocatalysi Methylene The experiments were performed independently with (Ulla
s/Mn-doped Blue Mn-doped ZnO particles and undoped ZnO and h and
ZnO noticed that the doped particles have mineralized the Dutta,
particles MB dye stuff more effeciently and briskly than the 2008)
undoped particles. 50% of MB dye was decolorized
in 5 mins with ZnO: Mn2+ and UV.
Photocatalysi Basic Blue It was noticed that N- hydroxy alkylated byproducts (C.
s/ZnO 11 (BB 11) were produced and BB 11 dye has encountered Lu et
oxidative degradation under UV irradiation, and •OH al.,
radical was major oxidant in this process. It was 2009)
observed that in 24 mins, 0.05 g/L of dye was
degraded to 1% approximately [1-(C/C0)]
Photocatalysi RhodaminB Photocatalytic action of the doped TiO2 films was (WU
s/Nd-doped evaluated under UV light by using the textile et al.,
TiO2 films industry pollutant Rhodamine B (RhB) and it was 2009)
noticed that in 30 mins of initial time 98% of RhB
dye was removed.
Photocatalysi Methyl By exercising porous-ceramic-assisted catalysts (Dan
s/ ZnO/ZTO Orange (MO) (CZnO/10ZTO) and in the presence of UV light witta
composites irradiation 50% of MO dye was mineralized in 1 hour yakul

16
 and roughly 95% of dye was mineralized in 3 hours. et al.,
The photocatalytic activity was intensified due to the 2013
ZTO islands, that were developed on the ZnO b)
nanorods.
Photocatalysi Organic dyes On irradiating the textile wastewater by sunlight, (Dan
s/ ZnO/ZTO 77% of COD elimination and 50% of photocatalytic witta
composites degradation efficiency was accomplished by yakul
exercising ZnO/15ZTO photocatalyst. The outcomes et al.,
were favourable when the ZnO/15ZTO catalyst was 2015)
utilized under solar light irradiation and about 16%
mineralization efficiency was escalated.
Photocatalysi Malachite The photodegradation of malachite green (MG) dye (Saiki
s/ green (MG) was deliberated by employing ZnO photocatalysts a et
synthesized synthesized by diverse methods and also, the al.,
ZnO influence different operating parameters, such as 2015)
initial dye concentration, light source, catalyst
loading, and pH on MG dye degradation was
examined. Under UV light, 93.75% of dye was
degraded.
Heterogeneo Leaf green The leaf green dye from the aqueous solution was (Aqui
us dye eliminated by exercising TiO2 photocatalyst no et
photocatalysi immobilized on polyethylene terephthalate (PET) al.,
s/UV-C/TiO2 plates and also in suspension form under UV light 2019)
(PET)/H2O2 irradiation. 70% of COD and 52% of TOC reduction
was achieved in UV-C/ TiO2 (PET)/H2O2 system.

2.4 Ceramic Membrane Filtration in Wastewater Treatment

Of late, the ceramic membranes are earning great recognition, because of their exceptional
features like pollution-free, superior chemical accuracy, regeneration, easy cleaning and a
long operating cycle in exercising wastewater treatment (Meabe et al., 2011). Previously, the
ceramic membrane had finite usage and was very costly (Fujioka et al., 2014). But, later on,

17
progress in membrane studies have ensued in the usage of membrane technology for several
motives and have befit cost-effective (Lee et al., 2015). Due to the fouling affair, the influent
water standards are to be examined prior to the ceramic membrane is used in the industrial
wastewater treatment operation.

Table 2.3. Application of membrane filtration for the treatment of various organic
contaminants in aqueous solution
Method Wastewater Results Ref.
Integrated Sulfur black, The outcomes have manifested the reduction of (Xu et
flocculation, 2,3-acidic absorbency of sulfur black, DSD acidic, 2,3-acidic al.,
cross-flow and DSD wastewater, and CODcr. At 0.1 MPa operating 2002)
microfiltration, acidic pressure and 1.0 µm ceramic membrane 93.3, 44.1
and ceramic wastewaters and 32.1% of absorbancy was achieved for sulfur
membranes black, 2,3-acidic wastewater, and DSD acidic
wastewaters respectively.
Three Textile dye The experimental outcomes have exhibited the (Barred
materialistic wastewater increment in permeate flux, a extremely miniature o-
ceramic cake layer formation on the membrane, and Damas
membranes of minimal flux removal. In addition, at the lowest et al.,
different cross-flow velocity, higher conductivity retention 2010)
molecular coefficients, and COD were acquired. The color
weight cut-offs and turbidity rejections were noticed between 98%
and 84% respectively.
Integrated Textile Under high pressure, very minimal color removal (Alvent
ceramic wastewaters and maximum flux decline were observed from osa-
membrane and containing a the experimental results. The solutions having deLara
ultrafiltration reactive dye exclusively RB5 were decolorized by more than et al.,
[Reactive 70% during filtration. On the addition of NaCl to 2014)
Black 5 the solution, minimal rejection of color and
(RB5)] and maximum decline of flux was also observed. The
NaCl authors have mentioned that this could be due to
the repulsion-attraction phenomena and membrane

18
 charge. It was also mentioned that the
performance of the ultrafiltration and the
membrane fouling effect was majorly influenced
by the electrostatic interactions between the
membrane materials and solute particles.
Ceramic Textile dye A significant decline in the color of 90% and 75% (Jedidi
microfiltration effluents of COD was observed. The researchers have et al.,
membrane compared and contrasted the permeate flux 2011)
(Manufactured performance with a commercial membrane and
with mineral observed the similarity.
coal fly ash)

In eliminating the pollutants from the wastewater the ceramic membrane follows two steps
(Ali et al., 2017). All the particles that are enormous than the membrane size are occluded by
the membrane, known as the self-retaining activity of the membrane. The smaller molecular
weight particles will be absorbed by the membrane due to electrostatic forces, chemical
bonds, and Vander Waals forces and this is known as the adsorption potential of the
membrane (Zhao et al., 2018). Depending on the pore size, the pressure-driven membranes
are divided into four types namely; microfiltration, ultrafiltration, nanofiltration, and reverse
osmosis (Jepsen et al., 2018). Excluding RO, the other three membranes are exercised in
industrial wastewater treatment applications (Van Geluwe et al., 2011). Based on the shape,
ceramic membranes could be classified into four types namely single-channel tubular, multi-
channel tubular, flat, and hollow fiber (Wang et al., 2018). In the wastewater treatment
process, the hollow fiber membrane is mostly employed. The flat membrane is widely used in
the water resources area and the tubular membrane is employed in solid-liquid separation
(Wang et al., 2018). Few recent studies on textile dye wastewater treatment using membranes
are discussed in table 2.3.

Various investigators used ceramic membranes and revealed that they are alternative to
polymer membranes and have extraordinary characteristics like physical, mechanical, lower
cleaning frequency, thermal stability, longer lifetime, and chemical resistance (Dow et al.,
2013; Karnik et al., 2005; Muthukumaran and Baskaran, 2014). Barredo-Damas et al., 2012

19
have treated textile mill effluents by tubular ceramic ultrafiltration membranes at various
operating constraints like molecular weight cut-off, pH, and transmembrane pressure. From
the results, it has been observed that, for higher pressures, up to pseudo-stable values the
permeate flux has been enhanced and 93% of turbidity, 96% of color, and 70% of COD
removal have been observed from wastewater.

2.5 Nanophotocatalysis Coupled with Membrane Filtration for

Wastewater Treatment

The life span of the membrane decreases when the membrane undergoes fouling because of
the precipitation or adsorption of molecules on its surface (Liu et al., 2010; Meng et al.,
2009). By applying physical cleaning, the removable fouling can be detached comfortably but
chemical cleaning is required for irremovable fouling. Reversible fouling and removable
fouling are similar. The reasons for the irremovable fouling and removable fouling are pore
blocking and loosely attached foulants. This fouling complication is more conspicuous in
ceramic and polymeric membranes. By integrating the photocatalytic system with membrane
separation, the fouling problem could be surpassed (Pidou et al., 2009; Zhang et al., 2006b).
In the integrated hybrid system, because of the photocatalysis process, the ceramic membrane
dismisses the suspended photocatalysts as well as degrade the organic contaminants.

The hybrid method could be used as an alternate in the treatment of several wastewaters for
the breakdown of various organic contaminants and removal of dyes like methyl orange,
direct black, congo red, methylene blue, etc. from textile dye wastewaters (Naresh Yadav et
al., 2018). Several researchers have worked on the hybrid system and the design and the
working conditions of each study are different from the other. In some research works, the
membrane was submerged in the photocatalytic reactor, and in other studies, both the systems
were combined sequentially (Donkadokula et al., 2020; Li et al., 2019). Most of the
researchers have utilized polymeric membranes for the combination with the photocatalytic
process and very few researchers have used ceramic membranes in the integrated process
(Song et al., 2018). Few recent studies on textile dye wastewater treatment using
nanophotocatalysis coupled with ceramic membrane filtration are discussed below in table
2.4.

20
Table 2.4. Application of nanophotocatalysis coupled with ceramic membrane filtration for
the degradation of textile dyes
Method Wastewater Results Ref.
Poly tetra fluoro Reactive At hydraulic retention time (HRT) of 4 h, 45– (Dam
ethylene (PTFE) Black 5 93% of TOC, 82–100% of color and 50–85% of odar
membrane (RB5) COD were removed et al.,
module 2010)
submerged in
TiO2 slurry
photocatalytic
reactor
Integrated C.I. Disperse 60-90% of dye degradation and 98% of COD (Busc
microfiltration Red 73 removal was achieved from the individual io et
process with photocatalysis system al.,
heterogeneous 2015)
photocatalytic
system
Integrated Congo red By utilizing PVP (ZnO-PVP-St) under stirring (Hair
photocatalytic dye stipulations and in the absence of agglomerations om et
membrane four kinds of Zinc Oxides were fused. At 0.3 g/L al.,
reactor ZnO-PVP-St loading 65 ± 1.0% and 100 ± 0.5% 2014)
of dye degradation was observed after
photocatalysis and nanofiltration respectively.
The minimal membrane flux removal and higher
photodegradation coherence in MPR were
achieved due to the presence of ZnO-PVP-St
Combined Methyl The study has revealed that the integration of (C. U.
ceramic Orange (MO) both systems has numerous advantages I.
membrane especially in terms of expenditure and Peng
system with compactness. From the obtained experimental et al.,
photocatalysis outcomes it was noticed that 90.4% and 77% of 2006)

21
 MO dye was degraded in the coupling and (Lee
cylindrical reactors respectively. et al.,
2001)
Double-side Methyl By employing UV irradiation on both sides of (Rom
active TiO2- Orange (MO) the membrane, the efficiency of the membrane to anos
modified photodegrade distinctive water contaminants et al.,
nanofiltration were assessed. The outcomes indicated that the 2012)
membranes in high water permeability and low adsorption-
continuous flow fouling propensity were noticed during the
photocatalytic decomposition of methyl orange in the
reactors composite NF membranes
Photocatalytic Acid Red 4 The conclusions of this research work comprise; (Wan
degradation a) Three and five times higher decomposition g et
combined with ratios for the dead-end system than the cross- al.,
TiO2 membrane flow system, b) On enhancing catalyst loading 2008)
assisted on a and light intensity, the decomposition ratio has
porous ceramic escalated, but at higher catalyst loading it
tube endured constant c) And with enhancing flow
rate the decomposition ratio decreased

The exotic materials like graphene oxide-TiO2 (rGO/TiO2) and altered TiO2 with an organic
shell layer were blended and fixed on the surface and pore structure of the monoliths
(ATHANASEKOU et al., 2013). The researchers have studied the impact of various operating
conditions including flow rate, feed concentration, and feed pressure on the membrane
permeability and the efficiency of contaminants breakdown. Further, they have focused on the
breakdown and removal of methyl orange (MO) and methylene blue (MB) under visible light
irradiation and near-UV/Vis, and continuous flow photocatalytic filtration. From the results, it
was observed that out of all the membranes, membrane N-TiO2-10 has exhibited excessive
MB dye removal efficiency i.e. 57% under UV. Moreover, another research group examined
the photooxidation of organic contaminants present in the wastewater by using silica/titania
nanotubes composite membranes. By using porous alumina support membranes, the
silica/titania membranes were composed from silica/titania sols. The water contact angle has

22
declined from 62° to nearly 5° in 80 minutes because of the surface membranes, which has
shown an intense affinity for water under UV irradiation. For Direct Black 168 dye at 100 min
of experimental operation, 73 and 66% of mineralization were achieved in individual
membrane separation and photocatalysis. Further, by merging both the systems, i.e., the
photocatalysis and the membrane separation process, 85% removal efficiency was attained.
From these results, it was concluded that the silica/titania nanotubes used in this research had
multifunctions such as breakdown, refinement of membrane flux in photooxidation, and
separation of organic contaminants in wastewater (Zhang et al., 2006a). Moreover, Mozia,
2010 explored the breakdown of toxic organic compounds in the presence of a photocatalytic
membrane reactor using immobilized TiO2 particles onto the surface of polymeric membranes
and their investigations showed that UV irradiation slightly damaged the polymeric
membranes.

2.6 Wastewater Treatment using Biofilms

Among all biological methods, biofilm technologies play a vital role in the treatment of
various wastewaters (Sehar and Naz, 2016). Biofilms are composed of several microbial
communities bounded in self-generated extracellular polymeric substance (EPS) matrices
(Naresh Yadav et al., 2020). The biofilm development has five important phases; i) The early
attachment of planktonic microbes to a solid surface or with one another in an aqueous media;
ii) Absolute fixation consequent to the generation of microorganism-moderated EPSs as
polyhydroxyl groups and along hydrogen bonding these polyhydroxyl groups seize bacteria to
the surface (van Belkum, 2007); iii) Development of monolayer mini colonies on the firm
surface as attached growth or suspended growth because of the replication of initial
colonizers; iv) Biofilm development into 3D form by utilizing the new planktonic bacteria and
also by binding the detritus from the adjoining surroundings, and v) diversification or
scattering by passive and active methods in which the matrix-encased biofilm cells transform
into planktonic bacteria through a cell-to-cell signaling procedure (Webb, 2009). Few recent
studies on textile dye wastewater treatment using biofilms are discussed below in table 2.5.

23
Table 2.5. Application of biofilm processes for textile dye wastewater treatment
Method Wastewater Results Ref.
Anaerobic biofilm Textile azo On using the primary Fenton reagent (Punzi
method combined with dyes concentration less than 10 mM H2O2 and 1 et al.,
photo-Fenton (Remazol mM ferrous ions, COD was diminished to 2015)
oxidation Red) lower than 18 mg/L. Eventually, the toxicity
was also reduced by the photo-Fenton
oxidation, but the final effluent consisted of
high concentrated NaCl. More than 90% of
absorbance and COD removal were
observed in this study. The obtained
experimental outcomes of this research
work have recommended the utilization of
photo Fenton oxidation after biological
treatment for the elimination of toxic and
organic pollutants from the textile effluents
Three-stage moving- Textile dye For the biological treatment, polyurethane- (Park
bed biofilm reactor wastewater activated carbon (PU-AC) (20% v/v) was et al.,
filled in each reactor and the activated 2010)
sludge was inoculated into MBBRs. At HRT
44 hr, 50% of color and 86% of COD was
removed by the MBBR process and this was
the significant results for the treatment of
dye wastewater
Dye-degrading Textile The researchers in this study have used (Kee
bacterial strains such wastewater sterile sludge as a seeding agent. From the et al.,
as Lysinibacillus experimental results it was observed that at 2015)
fusiformis strain ZB2, HRT of 24h, 46% of COD and 61% of color
Brevibacillus removal was achieved by the developed
panacihumi strain granules. The results have revealed that for
ZB1, Bacillus cereus efficient textile wastewater treatment such

24
strain ZK2, and as bacterial mixed cultures are highly
Bacillus pumilus strain promising.
ZK1

Factors that affect the formation of biofilm are nutrients, pH, temperature, the surface
topology of support media, velocity, turbulence, hydrodynamics, production of EPS, and
divalent cations (Ansari et al., 2017; Krivorot et al., 2011). To allocate the attachment
surfaces for biofilm development, the Solid Support Media (SSM) is incorporated in the
suspended growth reactors. The addition of SSM enhances the microbial concentration and
breakdown the pollutants as well (Pal et al., 2010). The carbonaceous materials, phosphorous,
trapped pathogens, nitrogen-containing compounds, and nutrients from the wastewater are
degraded by the various microbial populations present in the biofilm matrix. Advantages
offered by the biofilm-based wastewater treatment plants are flexibility in operation, less
space required, decrease in hydraulic retention time, the less effective over the environment,
increase in biomass weight, low sludge production, superior biomass residence time, and
superior capability to degrade complex compounds (Lewandowski and Boltz, 2011; Martin
and Nerenberg, 2012).

Ong et al., 2008 by employing the granular activated carbon-biofilm configured sequencing
batch reactor, evaluated the C.I. Acid Orange 7 (AO7) mineralization. The dimensions of the
SBCR was 20 × 20 × 20 cm and was split into two sections, specifically Multipurpose (MP)
and GAC compartments. Granular activated carbon (2.3 l) was used to fill the GAC
compartment and using an attachment the azo dye degrading microorganisms were attenuated
on GAC. To restraint the DO and to maintain efficacious mixing a mixer was established in
the MP compartment. To observe the ORP values and the pH, a redox meter and a pH meter
were kept in GAC and MP compartments respectively. By submerging the GAC into the
anaerobic bioreactor, it was disabled with microbes that degrade the azo dyes. Wastewater
containing 2 l of AO7 was fed into SBCR and operated for 24 h cycle time in the ratio of
3:20:0.45:0.15. At 625 mg/L of initial AO7 concentration, less than 0.25 mg/L DO, and in the
absence of outside carbon sources, the biological system has achieved almost absolute
mineralization of AO7.

25
2.7 Combination of Advanced Chemical and Biological Processes

Major chemical pollutants like pesticides, dyes, solvents, heavy metals, etc are considered
hazardous materials and major threats to the purity of water (Rasalingam et al., 2014).
Through wastewater treatment plants or in other ways the chemicals penetrate the aquatic
medium and substantial amounts of tenacious substances will be spread over to very long
distances from the pollutant's source point. Photodegradation and biodegradation are
considered as the most suitable methods for demolishing the noxious compounds in natural
water. Pesticides, phenols, aromatic hydrocarbons, etc can be degraded by using
photodegradation (Van Leeuwen, 1996). And in the biodegradation method, generally by
using the microbes, the pollutants are eliminated. Studies have revealed that the integration of
biological methods with the chemical oxidation processes will enhance the efficiency and
lower the operating costs (Oller et al., 2011). Few recent studies on textile dye wastewater
treatment using combined advanced chemical and biological processes are discussed below in
Table 2.6.

Rodrigues et al., 2014 worked on the combined Fenton's process and sequential batch reactor
(SBR) for the removal of organic matter and color from polyester, cotton, and acrylic dye
wastewaters. To minimize the operating costs and maximize the DOC and color removal, the
H2O2 and Fe(II) were applied in optimum dosage in the combined process. At persistent
temperature (25°C) the biological reactor was operated till 10 cycles (12 h/cycle). After
adjusting the pH to 7.0 in the first cycle, the biological reactor was supplemented with 2.5 L
of wastewater. The final volume was made to 5 L by adding 2.5 L of activated sludge. To
reimburse the quantity of treated effluent released, the reactor was supplemented with 2.5 L of
effluent. Using air diffusers, the DO content was enabled at 3 ± 1.3 mg O2/L and a mechanical
stirrer was utilized in the course of reaction stage. The oxidation-reduction potential (ORP),
temperature, and pH were frequently observed. Dissolved organic carbon (DOC), Chemical
oxygen demand (COD), Biological oxygen demand (BOD5) and total suspended solids (TSS)
were determined at the end of each cycle. Lab view 5.0 software was used to attain automatic
unit control and data acquisition. The combined system has shown significant results than
individual systems and has shown 99% of color, 91-98% of DOC, 83-95% of BOD, and 88-

26
98% of COD removal. Further, 24-39% of operating costs were reduced by the combined
system.

Table 2.6. Application of combined advanced chemical and biological processes for textile
dye wastewater treatment
Method Wastewater Results Ref.
Integrated Textile The integrated biological processes (C. oleophila) (Lucas
chemical and Reactive Azo and Fenton's process has decolorized 91% of RB5 et al.,
biological dye dye having an initial concentration of 500 mg/L. 2007)
process
Integrated Remazol The ozonation process acts as the pretreatment for (de
biological Black B dye degradation. At 500 mg/L of Remazol Black Souza
biofilm and B dye and pH 3-11, about 96% of dye removal et al.,
ozonation was achieved. For the biological treatment, the 2010)
dye removal has increased with an increase in
ozonation time
Combined up- Brilliant red The ozonation was used as a pretreatment method (X. Lu
flow X-3B azo dye in which BOD5/COD has enhanced from 0.1 to et al.,
biological 0.4 and the decolorization was achieved in 120 2009b)
aerated filter min for 34.08 mg/L of dye concentration. In the
and sequential combined system around 90% of COD removal
ozonation and 97% of decolorization were achieved.
process
Combined Dyeing and The wastewater was initially treated by the (X. Lu
sub-filtration printing biological process and followed by a sub-filter et al.,
and biological wastewaters method. From the experimental results, it was 2009a)
process observed that 90.9%, 92.5%, and 91% of average
turbidity, color, and CODcr were achieved.
Providencia sp Red HE3B The degradation and decolorization of the current (Phuga
. SDS (PS) dye the bacterial consortium (PS & PA) found to re et
and Pseudomo be quicker than the independent bacterial strain. al.,
nas Altogether in degradation and decolorization 2011)

27
aeuroginosa st process several important dye decolorizing
rain BCH enzymes (DCIP reductase, azoreductase, laccase,
(PA) veratryl alcohol oxidase) were inducted. In a 1 h
time and at 50 mg/L dye concentration 100%
decolorization was achieved.
Sphingobacter Direct Blue 100% of DBGLL (300 mg/L) dye was decolorized (Tamb
ium sp. ATM GLL by the isolated Sphingobacterium sp. ATM strain oli et
(DBGLL) in 24 h. Few other textile effluents and mixed dye al.,
effluents were also decolorized by the same strain. 2010)
At the time of DBGLL and other dyes
decolorization process, few enzymes (azo
reductase, riboflavin reductase, DCIP reductase,
laccase, veratryl alcohol oxidase) accountable of
degradation were introduced.

In a study, Shah et al. 2012 investigated the enzymatic degradation of Reactive Orange 13 dye
using newly isolated bacterial strain Alcaligenes faecalis PMS-1. The experimental results
have revealed that at static anoxic condition, 24.75 mg l-1h-1 average decolorization was
achieved; which is 38.13 times higher than the existing literature results. By using Michaelis–
Menten kinetics, the Michaelis constant (Km) and the maximum rate (Vmax) were found to be
27.1 mg l−1 h−1 and 105 mg l−1. At the time of RO 13 decolorization, NADH–DCIP reductase,
Tyrosinase, Veratryl Alcohol Oxidase enzymes were noticed.

2.8 Gaps identified based on the state-of-art review

From the reported literature, an enormous quantity of water is consumed by the textile
industries and also releases a large amount of wastewater having organic and inorganic
pollutants. To protect the environment from these pollutants and to reuse the used water, the
effluents are to be treated mandatorily using various technologies (advanced Physico-
chemical and biological). The techniques reported here are the best befitting options for
progressing wastewater at a small scale and also for real industrial wastewater treatment at a
large scale. Various wastewater treatment methods are needed to be integrated into the

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streamlined treatment of contaminated water and also to reach the discharge standards. The
gaps identified from the literature are; only a few studies have discussed treatment costs and
the best available technology, not entailing excessive costs that become arduous when there
are no-cost figures. The major gap identified in the literature is that the integration of
advanced oxidation processes (i.e. photocatalysis combined with ceramic nanofiltration) for
the dye wastewater treatment. The studies on textile dye wastewater treatment using biofilms
developed on solid support media are limited in the literature. The application of submersible
filtration in the presence of a photocatalytic reactor to reduce the membrane fouling was not
much discussed. In this research, two separate efficient systems were developed for dye
wastewater treatment. (i) Integrated photocatalysis and nanofiltration and (ii) Biofilms
developed on solid support media. The developed systems can be further used to carry out the
studies on; a) transition metal-doped photocatalysts; b) Biofilm coated filtration along with
photocatalysis unit to reduce the membrane fouling and maximizing extent of pollutants
removal; c) Surface coated photocatalysts onto the membrane to reduce the membrane
fouling; d) Various solid support mediums can be used for the biofilm development to treat
the wastewater and e) Treatment of mixed textile wastewater can be carried out using the
biofilms developed on various SSMs.

2.9 Problem statement and motivation

A large amount of dyes, nearly 5-10% of the annual universal production (ca. 107 kg), is
released as an effluent mostly by the paint and textile manufacturing industries (Lydakis-
Simantiris et al., 2010). These industries utilize large volumes of freshwater and also other
recalcitrant chemicals for textile processing. After the processing, large volumes of
wastewater is released into the environment. Most of these dyes are poisonous and also
carcinogenic, harms human and aquatic life (Lydakis-Simantiris et al., 2010). The majority of
the materialistic dyes are made-up of synthetic genesis containing multiplex aromatic
structures that forge them firmly even after simple oxidation and conventional treatment
(Herrmann et al., 2007; Lydakis-Simantiris et al., 2010; WU et al., 2009).

About 10-15% of the total dyestuff utilized in these industries are directly released into the
environment in the form of wastewater (Ouasif et al., 2013). Among several available dyes,

29
the azo dyes are environmentally unfriendly, mutagenic, and carcinogenic, and also they are
strongly resistant to degradation by the standard treatment methods and biological methods as
well. Furthermore, the non-destructive physical methods convert the organic contaminants
from one form to another form. The conventional treatment methods including
physicochemical, chemical, and biological techniques such as biosorption (Chen and Chen,
2009; Elisangela et al., 2009; Türgay et al., 2011), adsorption (Gupta et al., 2011), and
coagulation (Ellouze et al., 2011; Papić et al., 2004; Yang and McGarrahan, 2005) are
normally involved in high operating costs, lower efficiency, prolonged treatment time and
disposal issues. Because of these reasons, these techniques have limitations in usage.

Two methods were found to be efficient for the textile dye wastewater, namely; Integration of
photocatalysis with nanofiltration and biofilm-based wastewater treatment methods. The
difficulties associated with the existing techniques of textile dye wastewater treatment has
motivated to carry out the present research using the above two different methods.

2.10 Aim and Objectives of the study

This research work aims at developing an efficient hybrid system for the dye wastewater
treatment by the integration of photocatalysis and nanofiltration and also to develop an
efficient system for the biofilm development on solid support medium for the dye wastewater
treatment.

Objectives

 Development of a hybrid system for dye wastewater treatment by integrating

nanofiltration with photocatalysis.
 Optimization of various operating parameters such as pH, catalyst loading, and time
for the removal of dye pollutants using Response Surface Methodology (RSM).
 Development of an efficient system for the biofilm growth on solid support medium
for dye wastewater treatment.

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