Textile wastewater treatment by hybrid advanced oxidation processes

Textile wastewater treatment by hybrid advanced oxidation processes

Astrid Rahmawati1, Jenni Lie2, Chintya Gunarto3

1
D10406822, Department of Chemical Engineering, Taiwan Tech
2
M10606802, Department of Chemical Engineering, Taiwan Tech
3
M10606804, Department of Chemical Engineering, Taiwan Tech

Abstract
Textile wastewater is one of the fastest and largest growing industry in the world which consumes a large amount
of water and chemical, especially dyes in its process. As results, it contains high COD (150 – 35,000 mg/L) and
BOD (100 – 9625 mg/L) which are arduous to be degraded since it possess toxic and potentially carcinogenic to
environment. Therefore, a proper treatment is needed before their discharge. Several treatment methods such as
physical, biological, and chemical processes have been widely studied in textile wastewater treatment. Physical
treatment is commonly used for assisting particulate matter removal in pretreatment process of textile wastewater
treatment. It is usually followed by biological or chemical processes. Biological treatment is known as an
environmentally friendly process for the complete degradation of textile wastewater. However, it resulted less
efficiency of COD and color removal. Advanced oxidation processes (AOPs) are one of chemical treatments
which known as promising alternative for oxidizing the organic compounds of textile wastewater. It could remove
color and COD content over 90%. Ozone, H2O2, and Fenton processes are the most commonly used as AOPs
reagents. In order to enhance the degradation efficiency of AOP, the combination or hybrid method exhibits a
good approach that can be applied for color, COD, and BOD removal in textile wastewater treatment. Moreover, it
is also potentially applied in water recycle technology for water conservation in textile industry. This mini-review
paper suggests the possible hybrid process to treat the effluent generated from textile industry.

1. Introduction
Textile industry is one of the largest industries in the world and consumes massive amounts of water and
chemicals in its processing. Approximately 21-377 m3 of water is needed to produce one ton of textile product
(Asghar et al., 2015). The chemical consumption used generally varies from 10% to over 100% of the weight of
the cloth (Asghar et al., 2015) and the chemical loads are generated mainly due to the residues from preparation,
dyeing, finishing, sizing, and other operations (Ozturk et al., 2009). Most pollution in textile wastewater comes
from dyeing and finishing processes, such as bleaching, dyeing, printing, and stiffening (Stefan, I.M., 2018).
According to the World Bank prediction, dyeing and finishing treatment in textile industry given to a fabric
produces around 17-20 % of industrial wastewater (Kant, R., 2012). Around 72 toxic chemicals have been
identified in water solely from textile dyeing, 30 of which cannot be removed. It has been recorded that
approximately 700,000 tons of dye are produced each year in all over the world and 280,000 tons of the synthetic
dyes are discharged into waste stream through during manufacturing or processing operation (Riera et al., 2010;
Eren, Z., 2012). Some of these dyes are degraded naturally, yet some need special treatment since it cannot be
degraded naturally (Gupta and Suhas, 2009). As results, high organic compounds are produced from textile
effluents (Asghar et al., 2015; Ghodbane and Hamdaoui, 2009). It leads to significant amount of environmental
degradation and human disease. It has been indicated that about 40% of globally used colorants that contain
organically bound chlorine a known carcinogen. Almost all of organic materials found in the wastewater from
textile industries are a great concern in water treatment since it can react with many disinfectants especially
chlorine (Kant et al., 2012). Furthermore, discharge of even a small quantity (ca. 1 mg/L) of dye in the effluent is
not acceptable and could perform toxic and potential carcinogenic to microorganisms, aquatic life, and human
beings (Ghodbane and Hamdaoui, 2009; Turhan et al., 2012). Therefore, an adequate treatment strategy is
required to meet the pollution control requirements before they can discharge into receiving water bodies (Chang
and Chern, 2010).
Many treatment processes including biological, physical, chemical, physicochemical, and hybrid treatment
have been reported to treat textile wastewater in an efficient and economical way (Turhan et al., 2012; Holkar et
al., 2016; Stefan, 2018). Since dyes are designed to resist degradation, biological treatment methods are less
efficient in decolorization and degradation processes due to the sludge formation [Turhan et al., 2012; Asghar et
al., 2015]. It also inhibits microbial activity and may cause failure of biological treatment process in some cases
(Ozturk et al., 2009). Membrane bioreactor (MBR) technology is the combination process between biological and
physical process in one system (Gundogdu et al., 2017). It is a promising technology for textile wastewater
treatment due to its capability to degrade organic compound by biological process and simultaneously purify the

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 Textile wastewater treatment by hybrid advanced oxidation processes

wastewater with filtration. MBR has been applied for dye-degrading microorganisms and involving simultaneous
filtration in textile wastewater treatment processes (Hai et al., 2006). It has ability to remove 60-95% COD and 60-
97% color depend on the type of textile wastewater. Recently, anaerobic MBR method has become an attractive
option for wastewater treatment due to its important advantages over aerobic MBR such as low energy
consumption and less sludge production.
Oxidation method is known as advanced oxidation processes (AOPs) including ozonation, photocatalysis,
electrochemical oxidation, Fenton and Fenton-like processes, the use of microwaves, ultrasound, and wet
oxidation processes (Asghar et al., 2015; Dewil et al., 2017). AOPs belong to green oxidation processes since it
generates a complete mineralization such as carbon dioxide, water, and mineral acids (ca. HCl). AOPs perform
highly reactive oxidizing agent hydroxyl radical (HO·), which completely destroys the recalcitrant components and
toxic chemicals contained in textile wastewater (Holkar et al., 2016; Dewil et al., 2017). Among AOPs, Fenton has
gained much attention due to its rapid formation of HO• radicals in acidic condition based on the following
chemical reaction: Fe2+ + H2O2 → Fe3+ + HO· + HO-. It promotes oxidation of complex organic pollutant by
promoting H2O2 decomposition which resistant to biological degradation of both soluble and insoluble dyes
(Holkar et al., 2016). Several studies of Fenton oxidation combined with other AOPs has been discussed (Asghar
et al., 2015; Chong et al., 2012). However, there are some drawbacks of these process such as large sludge
generation of iron (Babuponnusami and Muthukumar, 2014), high cost of H 2O2 and excess used of chemicals
especially H2O2 (Hassan et al., 2012). Furthermore, handling and storage of bulk quantities of H 2O2 could make
the process harmful and not economically viable for textile wastewater treatment (Asghar et al., 2015). Ozone is
generally used for decolorizing dye wastewaters since it can effectively break down the conjugated double bonds
of dye and other functional groups, namely complex aromatic rings of dyes (Holkar et al., 2016). The main benefit
of the ozonation process is that ozone can be applied in its gaseous phase, hence does not increase the volume
of wastewater effluents and does not produce a large amount of sludge. Nevertheless, the main shortcoming of
using ozone is that it may generate toxic byproducts from biodegradable dyes in textile wastewater (Miralles-
Cuevas et al., 2017). Cost is a challenging issue in the ozonation process due to its short half-life of 10 minutes in
water at neutral pH (Gosavi and Sharma, 2014). As above mentioned, textile-dyeing and finishing processes
consume huge amount of water about 334 – 835 liter water/kg textile (Bisschops, 2003). Therefore, water
conservation or water reuse is a challenging issue to manage water resource mainly freshwater as sustainable
resources. The main goals of this mini review are to study characteristics of textile wastewater and the feasible
process to remove dyes and recalcitrant organic pollutant containing textile wastewater, to elaborate AOPs and
hybrid process for textile wastewater treatments, and to consider the possibility of water reuse or water
conservation of textile effluent as sustainable resources.

2. Textile industry wastewater

Textile industry is one of the key role in the development of any country. Various raw materials of textile
industries such as cotton, woolen, and synthetic fibers have been used globally. Around 80% of the total
production of 1, 300,000 tons of dyestuff are consumed regarding to textile industry due to high demand for cotton
and polyester (Mistry et al., 2017; Holkar et al., 2016). Dyes containing textile wastewater tremendously affect
photosynthetic function in plant. It has negative effect on the aquatic life due to low oxygen consumption and light
penetration (Holkar et al., 2016). Textile sector also plays a vital role in Pakistan’s economy since it is providing
employment to 38% of people as well as it is vital source of foreign exchange (Siddique et al., 2017). Around 65%
of export country is supplied by the textile sector alone (Bauer et al., 2001). Globally, textile industry accounts for
46% of total production which many industries are working by their production (Siddique et al., 2017). It has been
reported that textile products are exported and contribute 9% of gross national product (GNP) (Sudipta et al;
2005). The main processes in the textile industries involve dyeing and finishing processes such as bleaching,
dyeing, printing, and stiffening (Holkar et al., 2016). These processes have created a huge pollution problem
since it is one of the most chemically intensive industries in the world (Kant et al., 2012). Among other countries,
China is the largest textile producing and exporting country in the world. It has been reported that 390 million tons
of sewage water is producing annually in China (Siddique et al., 2017). Approximately 51% is produced by
industrial sector and this rate is increased by 1% annually (Ho and McKay, 2003). Based on the rough prediction,
textile sector has a major contribution around 51% of the sewage wastewater as 70 billion tons per year of
wastewater is coming out from dyeing process (Siddique et al., 2017). This wastewater contains highly pollutant
and it is not adopted to discharge this water without any pretreatment. This highly pollutant in textile wastewater
causes water resources not worthy to use for other purposes.
2.1. Major pollutants in textile wastewater
Three major pollutants found in textile wastewater involving color, hazardous toxic metals, and inorganic
chemicals from dyeing and finishing processes (Kant et al., 2012; Mondal et al., 2017). The presence of color in
the wastewater is one of the main problem especially in textile industry which visible to human eyes even at very

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 Textile wastewater treatment by hybrid advanced oxidation processes

low dye concentration. Most of these dyes are chemically stable, non-biodegradable, and unaffected by light. The
presence of toxic metals in the textile wastewater is other major problem. It may come as impurities with the
chemicals such as caustic soda, sodium carbonate, and salts during processing or it may be present in dyestuff
viz. metalized mordent dyes. Moreover, the presence of chromium compounds and heavy metals such as arsenic,
copper, lead, cadmium, nickel, mercury, and cobalt and other auxiliary chemicals also make the textile effluent
highly toxic. Other than that, harmful chemicals found in textile wastewater may be formaldehyde based dye fixing
agents, hydrocarbon based softeners and non-biodegradable dyeing chemicals (Kant et al., 2012). The use of
inorganic sodium salts such as sodium chloride and sodium sulfate in dyeing processes in textile wastewater
could directly increase total dissolve solids (TDS), total solids (TS) and it is difficult to remove by conventional
treatment methods (Mondal et al., 2017).
2.2. Characteristics of textile wastewater
The main parameters in textile wastewater are COD, BOD, TDS, TSS and pH. Table 1 presents the typical
wastewater characteristics of textile effluents from some textile industries.
Parameters Value
COD (mg/L) 150 – 35,000
BOD (mg/L) 100 – 9625
TDS (mg/L) 1800 – 109000
TSS (mg/L) 100 – 5000
pH 6 - 10
Color (Pt-Co unit) 50 – 2500
Table 1 Characteristics of textile dyeing wastewater (Ghodbane and Hamdaoui, 2009; Kalra et al., 2011;
Mistry et al., 2017)

3. Treatment methods of textile wastewater

Before textile wastewater is being discharge into water bodies, many treatment methods including physical,
chemical, biological, AOPs, and hybrid process have been studied to treat it in an efficient and economical way.
3.1. Physical treatment
There are several types of physical treatments such as adsorption, flotation, filtration, flotation and
sedimentation (Kant R, 2012; Siddique et al., 2017). Adsorption has attracted much attention due to their better
decolorization efficiency for wastewater containing a variety of dyes, high affinity of the adsorbent, biodegradable,
reusable, and low cost (Holkar et al., 2016; Hossini et al., 2017 ). Adsorbent regeneration ability is noteworthy to
be considered during the selection of an adsorbent for decolorization process (Jadhav and Srivastava, 2013).
Activated carbon, clay, bentonite, zeolite, chitosan, biomass, and starch are commonly used as adsorbents in
textile wastewater (Markandeya et al., 2017). They noted that zeolite could reach 93% removal of disperse
orange dye. However, the use of these adsorbents had limitation for several problems such as its regeneration or
dumping, sludge generation, and high price of adsorbet (Gupta et al., 2011). Filtration methods such as
ultrafiltration, nanofiltration, and reverse osmosis have been reported to recover and reuse a water (Asghar et al.,
2015). For textile industry, the use of membrane performs a great potential for the recycle of reactive dyes and
simultaneously decrease the BOD, COD, and color from the textile effluent (Chollom et al., 2015). Liang et al.
(2014) reported that nanofiltration can persistently remove dye using combination methods like coagulation-
flocculation as chemical treatment process. These filtration methods are effective for salt removal and it can be
applied for textile wastewater treatment. However, the possibility of membrane fouling, polluted concentrate
forming, and high cost due to high pressure condition have always become the challenging issues(Holkar et al.,
2016). In textile wastewater treatment, filtration and flotation methods are commonly used to remove fibers.
Flotation treatment is a process of particles removal in the water using small bubble produced by air injection and
based on density dissimilarity (Siddique et al., 2017).
3.2. Chemical treatment
In this process, addition of chemical is used to enhance textile wastewater characteristics. Chemical
consists of two main treatments namely AOP and oxidative process. For oxidative treatment, F 2, Cl2, Br2, KMnO4,
ClO- are used as oxidizing agents to remove color. AOPs have several types, such as Fenton, ozonation,
hydrogen peroxide, UV radiation, and ion exchange (Siddique et al., 2017). Table 2 shows textile wastewater
treatment using AOPs is more efficient than conventional oxidation process, although it requires high operational
cost.
Chemical treatments
Parameter
AOPs Conventional oxidation process
Oxidizing agents Hydroxyl radical (OH·), H2O2, O3 F2, Cl2, Br2, KMnO4, ClO-
Cost ($ m )-3
5 - 6.5 0.3 - 3
COD removal 92 - 99% 54%

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 Textile wastewater treatment by hybrid advanced oxidation processes

Color removal 85 -100% 52%

Sludge generation Yes Yes
Table 2 Comparison of Chemical Textile Wastewater Treatment (Malik et al., 2017)
There is a combination process between physical and chemical treatments, called physicochemical.
Coagulation-flocculation and coagulation-sedimentation are categorized by physicochemical treatment. These
process are beneficial for the decolourization of wastewater containing disperse dyes (Holkar et al., 2016). The
advantages of this process are low cost and simple maintenance (Liang et al., 2014). Coagulant concentration,
pH of wastewater, and retention time are the significant parameters that has to be controlled in the
physicochemical process (Malik et al., 2017; Hassanzadeh et al., 2017; Xiao et al., 2017).

3.3. Biological treatment

Biological treatment is a process for wastewater by combining the bacteria, fungi, algae, and yeast due to its
high microbial activity that may decrease toxicity effect and enhance stability process (Abiri et al., 2017). It is used
for mineralization of biodegradable organic compound only (Pazdzior et al., 2017). Biodegradation regard to
microorganism is divided into two condition namely anaerobic biodegradation and aerobic biodegradation.
Anaerobic is a condition that occurred in the absence of oxygen, while aerobic occurred in the presence of
oxygen. Anaerobic process and biofilm are mostly used in textile wastewater treatment (Spagni et al., 2012). Abiri
et al. (2017) reported that anaerobic process has been successfully applied for reduction reactive and disperse
dyes, yet it produces aromatic amines that potent highly toxic to environment. Other advantages of anaerobic
process are it can handle high organic loads, it does not require aeration, and it generates less sludge compared
to the aerobic process. In other hand, aerobic process depends on chemical structures of the degradation
products and enzyme in the system that may or may not work while in some cases of toxic organic molecules
remain in the effluent (Rodrigues da Silva et al, 2012). Sarvajith et al. (2018) showed that up to 100% of color
removal and 98% TOC removal can be achieved through biological treatment with a long retention time of 80
days. COD in dye wastewater is difficult to remove by using biological treatment, therefore high retention time is
needed (Punzi et al., 2015). Several kinds of biological treatment are membrane bioreactor, trickling filter,
granular biomass systems, etc.
MBR has been widely used for textile waste water treatment due to its high performance. It is a combination
process of suspended growth process and membrane separation system by filtration (Metcalf and Eddy,
2014).The mechanism of color removal in MBR technology was adsorption of dye molecules onto biomass. MBR
offers some advantages, such as small footprint, low maintenance, higher treated water quality, higher removal of
nutrients and organic, as well as lower sludge production (Jegatheesan et al., 2016). However, MBR has
operational problem such as fouling caused by fine pore diffused aeration and by fine particle solid. Membrane
fouling can be avoided by cleaning, addition of antiscalant or powdered activated carbon and air backwashing (Li
et al., 2016). Aerobic and anaerobic MBR treatments for textile wastewater are shown in Table 3. MBR could
achieve more stable effluent quality than conventional anaerobic process.
Process COD removal (%) Color removal (%) HRT (h) TMP/flux Reference
Aerobic 60 - 95 87 n.a. 0.4 bar, 30 L/m2h Brik et al., 2006
Aerobic 98 100 48 0.07 - 0.35 bar Friha et al., 2015
Aerobic 90 60 - 75 6 0.05 - 0.1 bar Hoinkis et al., 2012
Anaerobic 90 94 24 1.8 -14.4 L/m2h Lin et al., 2013
Table 3 Aerobic and anaerobic MBR treatment for textile wastewater
Hydraulic retention time (HRT) and transmembrane pressure (TMP) are the main parameters of MBR
operation. Anaerobic MBR was very effective process for COD and TSS removal, for high organic strength and
highly particulate wastewater treatment (Jegatheesan et al., 2016). Determination of methods depend on the
amount and concentration of textile wastewater, as well as characteristics of dyes that will be treated. A single
wastewater treatment will combine each other or it called hybrid in order to achieve effective and efficient textile
wastewater treatment (Pesoutova R, 2011).

4. Advanced oxidation processes (AOPs)

The organic compounds contained in textile wastewater have detrimental effect to environment since it is
toxic and potentially carcinogenic to humans, animals and plants. Therefore, an efficient treatment is needed to
remove those contaminants that not treatable by conventional technique such as biological processes due to the
arduous degradation of contaminant in textile wastewater. AOPs has been known as promising alternative of
wastewater treatment processes to degrade the toxic organic compounds. It is the oxidation processes involved
the generation of adequate amount of hydroxyl radicals (•OH) which categorized as powerful oxidant to attack
most of organic compounds become carbon dioxide, water and mineral acid. The dot (•) indicates the unpaired
electron present in outer orbital of molecule (Metcalf and Eddy, 2014). So, it becomes very reactive and react

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 Textile wastewater treatment by hybrid advanced oxidation processes

rapidly with the electron-rich organic compounds called electrophiles (electron-loving). Hydroxyl radical has high
oxidation potential of 2.80 V and the oxidation rate is 106 – 1012 times faster than using conventional oxidant such
as hydrogen peroxide and potassium permanganate (Holkar et al., 2016). AOPs promote a sustainable and green
wastewater treatment technology since it produces an environmentally friendly products such as CO 2, H2O and
minerals. Compared with conventional oxidation process, AOPs has higher degradation efficiency and it requires
less energy.
AOPs are classified based on the process to generate hydroxyl radicals as presented in Table 4. The
chemical oxidation method in AOPs generate hydroxyl radical from ozone (O3), hydrogen peroxide (H2O2) and its
combination with iron ions (Fenton) and/or catalyst such as TiO 2. The photo-chemical method is AOPs with UV
light assisting to produce hydroxyl radical from ozone or peroxide and also its combination with Fenton method.
The sono-chemical uses ultrasound process for hydroxyl radical generation, while electrochemical uses electrode
to improve the decomposition efficiency of dyes. In this review, we elaborate the hybrid AOPs based on the
hydroxyl radical resources specifically ozone, hydrogen peroxide, and Fenton. Table 4 shows the classification of
AOPs based on the sources applied for the ·OH generation.

Methods Type of AOPs References

Chemical O3 Boczkaj et al., 2017; Hassaan and Nemr, 2017
H2 O 2 Zuorro and Lavecchia., 2013
Fenton Babuponnusagazenkmi and Muthukumar, 2014
Catalyst (TiO2) Dewil et al., 2017
Photo-chemical O3/UV Hassaan and Nemr, 2017
H2O2/UV Zuorro and Lavecchia., 2013
Fenton/UV Babuponnusami and Muthukumar, 2014
O3/H2O2/UV Bilinska et al., 2017
Sono-chemical US+H2O2 Eren, 2012
US+O3 Eren, 2012
US+Fenton Babuponnusami and Muthukumar, 2014
Electrochemica Electro Fenton Ganzenko et al., 2014, Babuponnusami and
l Muthukumar, 2014, Dewil et al., 2017
H2O2 electrochemically Dewil et al., 2017
Table 4 Classification of AOPs
4.1. Ozonation
The chemical oxidation using ozone which called as ozonation is one of the most suitable and effective
process for color removal in textile effluents. It decomposes organic chemical into biodegradable compounds
such as ketone, aldehyde or acids. The advantage of ozonation is no sludge production, it is categorized as
strong oxidant with high oxidation potential 2.08 V (Table 4), it does not raise the volume of wastewater since it
can be used in gas phase, and low operational cost. A high pH, the reaction of hydroxide ion and ozone leads to
produce super-oxide anion radical O2 and hydroperoxyl radical. Boczkaj et al. (2017) reported that COD
degradation using O3 treatment at 25°C for 221.1 min was 39%, while the BOD 5 degradation was 45%. When the
temperature process increased to 40°C, the COD and BOD degradation decreased to 36% and 37%. However,
the solubility of ozone in liquid phase is higher in lower temperature thus increasing the mass transfer to the liquid
phase. The decomposition process using ozone become faster under alkaline condition of pH > 8.
Decolourization of dyes using ozonation process with applied ozone dose of 1.96 g/L at pH 12 for 10 minutes has
been reported by Bilinska et al. (2017). They found that the decolourization efficiency of dyes RY145, RR165, and
RB221 in those process condition were 87.5%, 90.7% and 97.6%, respectively. They proved that the maximum
decomposition efficiency of dyes was reached at alkaline pH (~12) and ozone does not effective at acid and
neutral condition. They also reported that the decolourization efficiency of dyes decreased to 5-15% with assisting
of UV light in ozonation system. By adding H 2O2 in ozonation system, the degradation of organic compound
(COD) was only increased to 4 – 7% compared with ozone solely. It was due to the increasing of reaction rate
constant as well as the larger amount of HO• for oxidation, but the raising COD degradation was not significant.
The oxidation mechanism depends on the molecular structure of organic compounds contained in dyes
wastewater. No additive effect and interaction of UV and H2O2 in ozonation. The higher concentration of H2O2 and
the smaller of color reduction in ozonation (because of the scavenging effect in alkaline condition) leads to
produce hydroperoxyl radical which less sensitive than hydroxyl radicals (Bilinska et al., 2017;
Babuponnusagazenkmi and Muthukumar, 2014).
O3 + 2H+ + 2e → O2 (1)
3O3 + H2O → 2 •OH + 4O2 (2)
•
OH + H2O2 → H2O + HO2• (3)

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 Textile wastewater treatment by hybrid advanced oxidation processes

4.2. Hydrogen peroxide

The other hydroxyl peroxide resources which can be used in AOPs is hydrogen peroxide (H 2O2). The use of
H2O2 as oxidation agent delivers some advantages such as it need lower cost operation than ozone since the
reaction occurred in liquid phase, it is cheaper than ozone and similar degradation efficiency with ozonation, and it
generates less sludge formation. Zuorro and Lavecchia (2013) have been evaluated the UV/ H 2O2 AOPs for the
degradation of diazo dye reactive green 19 in aqueous solution and found that neither H2O2 nor UV alone has a
good oxidation effect on RG19 removal. The degradation of dyes are more intense when they are combined.
Hybrid of UV/ H2O2 has successfully reached 99% dye decolourization of RG19 within 15-60 minutes. According
to the reaction 3, the reaction of hydrogen peroxide with hydroxyl radical produces hydroperoxyl (HO 2•) which less
reactive, therefore the rate of dye destruction would decrease progressively. The maximum oxidation rate
constant was reached at pH 6, it represents the optimum pH for hybrid UV/H2O2 process. The rate of
demineralization was lower than decolourization and the maximum demineralization obtained using UV/ H 2O2 was
63.5% in ca. 20 minutes. It may be due to the higher stability of aromatic ring structures in dye molecule
compared to the azo bond regions, and/or to their ability to stabilize intermediates product during the photolysis
process. However, the UV/H2O2 process leads to higher dye removal efficiency compared to the photocatalytic or
microbial degradation of RG19 (Zuorro and Lavecchia, 2013).
Dye + hv → products (4)
H2O2 + hv → 2 HO• (5)
Dye + HO• → products (6)
4.3. Fenton
The reaction of peroxide (commonly H2O2) with ferrous ion (Fe2+) assists to generate hydroxyl radical (HO•)
appropriate with reaction 7. This process was introduced by H.J.H. Fenton in 1894. He developed tartaric acid
oxidation using H2O2 that has been activated by ferrous salts. As shown in reaction 8 which called as Fenton-like
reaction, it allows Fe2+ regeneration in an effective cyclic mechanism. Reaction 8 shows the production of
hydroperoxyl radicals that may also attack the organic compounds. The iron ion acts as catalyst, therefore the
iron added in small amount whereas the hydrogen peroxide is consumed continuously to produce hydroxyl and
hydroperoxide radicals.
Fe2+ + H2O2 → Fe3+ + OH- + HO• (7)
Fe3+ + H2O2 → Fe2+ + H+ + HO2• (8)
Fe2+ + HO• → Fe3+ + OH- (9)
Fe2+ + HO2• → Fe3+ + OH2- (10)
Fe3+ + HO2• → Fe2+ + O2 + H+ (11)
HO• + HO• → H2O2 (12)
HO• + H2O2 → HO2• + H2O (13)
HO2• + HO2• → H2O2 + O2 (14)
HO• + HO2• → H2O + O2 (15)
2H2O2 → 2H2O + O2 (16)
Reaction 8 – 11 shows the rate limiting steps of consumed hydrogen peroxide reaction and ferrous ions
regeneration from ferric ions, while reaction 12 – 15 represents the Fenton process and radical-radical reactions.
The decomposition reaction of hydrogen peroxide as shown in reaction 16 leads to bulk oxidant exploitation thus
increase the treatment cost. Fenton process offers some advantageous such as it can be carried out at room
temperature and atmospheric pressure, the required chemicals are available, easy to store and handle, and safe
for environment. The pH of the solution is one of the important factor of Fenton process. The maximum organic
compounds of degradation using Fenton treatment was achieved at pH around 3 (Babuponnusami and
Muthukumar, 2014; Rivas et al. 2001). The reaction of Fenton decreased at higher pH since the presence of
relatively inactive iron oxohydroxides and the formation of ferric hydroxide precipitate. It caused a less free iron
ions to generate hydroxyl radicals. Increasing pH also make the oxidation potential of hydroxyl radicals
decreased. At pH below 3, the degradation efficiency decreases. It was due to the formation of iron complex
compound [Fe(H2O)6]2+, while the peroxide become solvated in the rich amount of H + ions to form stable oxonium
ion [H3O2]+. That ion reduces the reactivity with ferrous ions. Therefore, buffer solution is needed in Fenton
process to control the pH solution such as acetic acid or acetate buffer to give the maximum oxidation efficiency.
However, the buffer reaction increases the operational costs. The optimum concentration of ferrous ion and
hydrogen peroxide required in the Fenton process depend on the COD, BOD, and dye concentration contained in
wastewater. According to Babuponnusami and Muthukumar (2014), the optimum temperature of Fenton Process
was 30°C but the reaction is exothermic so it can rise over 40°C, thus cooling is recommended. Due to the sludge
production during Fenton process, the chemical coagulation is recommended after Fenton oxidation to control the
soluble ion concentration in the specified limit. Hsing et al. 2007 reported that decolorization and TOC removal
was in the order of O3 = Fenton < O3/UV < O3/TiO2 when the initial pH of Fenton process at 3 and 7 for other

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 Textile wastewater treatment by hybrid advanced oxidation processes

processes. It was not in agreement with Azbar et al. (2004), as shown in Table 6 the color and COD removal
order of coagulation < H2O2/UV < O3 < O3UV <Fenton < O3/H2O2/UV. Based on the report by Weschenfelder et al.
(2017), the organic compounds (COD) degradation treatment has been ordered H 2O2/UV < O3 < Fenton < O 3UV.
Therefore, it can be conclude that the decolorization and organic compound removal in the textile wastewater
depends on the pH condition, concentration of oxidant and catalyst, time, dyes and concentration of organic
compounds.
Treatment methods pH O3 (g/h) H2O2 (mg/L) FeSO4 (mg/L) Color removal (%) COD removal (%)
Coagulation 8.5 - - 350 49 60
O3 9 2 - - 90 92
O3/UV 9 2 - - 93 94
H2O2/UV 3 - 300 - 85 90
O3/H2O2/UV 3 2 200 - 96 99
Fenton 5 - 300 500 94 96
Table 5 Polyester and acetate fiber dyeing effluent containing 930 mg/L COD and 375 mg/L BOD 5 at
pH 9.2 (Azbar et al. 2004)

5. Water conservation from textile wastewater

Textile finishing industry is the second biggest water-consuming sector in Europe, after agriculture. Washing
step of finishing process consumes high amount of water around 334 – 835 liter water/kg textile (Bisschops and
Spanjers, 2003). The recycling process of textile wastewater will be very profitable since it can minimize water
consumption in the selected textile industry in terms of technology involved economics and associated impacts.
From this review, it is possible to reuse treated wastewater in textile production process using AOPs. The reused
water must fulfill the water quality requirement for textile plant and the water quality requirement for washing
process as presented in Table 6.
Parameters Max. level
Color None visible
COD (mg/L) 200
pH 7.0 - 8.0
Total hardness (ppm CaCO3) 100
Chloride (mg/L) 500 - 2000
Fe (mg/L) 0.1
Cu (mg/L) 0.05
Cr (mg/L) 0.1
Table 6 Water quality requirement for washing off processes (Bisschops and Spanjers, 2003)
According to the water quality standard for washing process, the allowed iron and copper content in water
process is very low, less than 0.1 mg/L and 0.05 mg/L, respectively. It is due to the ions of certain transition
metals such as Fe, Cu, and Mn can precipitate dyes, or form complexes with them, dulling or even changing their
shade. Fenton process is not suitable process for recycling textile wastewater due to it produce large sludge of
iron. As mentioned, Fenton and Fenton-like processes use Fe, Cu ions, and hydrogen peroxide as oxidant.
Therefore, the appropriate AOP that can be applied in recycling process is the process that is not using metal
ions, those are ozonation and hydrogen peroxide. Nadeem et al. (2017) reported a study on the polishing of
biologically treated textile wastewater through AOPs and recycling for wet processing. They said that biological
treatment cannot remove the color of textile wastewater, thus they used AOPs to enhance the color and COD
removal in treated wastewater. As results, UV/H2O2/O3 were recommended for recycling purposed of textile
wastewater since it gives high efficiency of decolourization and COD removal and it does not have effects on
fabric quality during recycling of supernatant. As shown in Table 7, the highest operating cost of AOP is
O3H2O2/UV but it also gave the best results of color and COD removal of textile wastewater.
Process Cost ($ m-3) Color removal (%)
O3 5.28 90
O3/UV 6.38 93
H2O2/UV 1.26 85
O3H2O2/UV 6.54 96
Table 7 Operation cost for AOPs treatment (cost of UV lamp and labor are excluded) (Azbar et al.,
2004)
Textile wet process uses chemicals which is mostly organic compounds. The COD should indicate the
organic compounds in wastewater, but some chemicals cannot be detected by COD analysis. They may have
oxidation potential which the small amount of the chemicals can deteriorate the quality of the product. Therefore,

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 Textile wastewater treatment by hybrid advanced oxidation processes

further process is recommended to purify the reused water and remove the non-essential component such as
organic compound and inorganic ions in the water. According to the array of potential hybrid technologies and the
available cost information, it can be proposed that biological after AOPs treatment appear to be the most
promising techniques to treat and recycle the textile wastewater. Biological processes are often the preferred
treatment for treating wastewater. They considered to have low environmental impact and costs compared to
other treatments due to it doesn’t require any addition of chemical and reasonable amounts of energy. As
mentioned earlier, membrane bioreactor (MBR) technology has shown a promising approach for industrial water
reuse due to it has very high quality recyclable treated water, small footprint, low maintenance, and lower sludge
production (Jegatheesan et al., 2016). It was reported that MBR have been applied for dye-degrading
microorganisms and involving simultaneous addition of adsorbent in textile wastewater treatment processes (Hai
et al., 2006). Aerobic MBR has been applied in textile wastewater for few years ago until now since it has ability to
remove 60-95% COD and 60-97% color depend on the type of textile wastewater. Recently, anaerobic MBR
method has become an attractive option for wastewater treatment due to its important advantages over aerobic
MBR such as low energy consumption and less sludge production. It has been reported from several studies that
anaerobic MBR performs an outstanding method for high organic strength and particulate wastewater in textile
wastewater treatment. It was very effective for COD and TSS removal which resulted more than 90% COD was
removed when the organic loading rate (OLR) was in the range 2-15 kgCOD/m3d (Ivanovic and Leiknes, 2012; Lin
et al., 2012). Furthermore, the operational costs of the anaerobic MBR were lower than aerobic MBR (Achilli et
al., 2011). It was due to large sludge management in the aerobic MBR. Table 9 shows the overall features of
aerobic and anaerobic MBR technology for wastewater treatment. Some advantages of anaerobic MBR over
aerobic MBR technology such as low energy requirement, less sludge production, and produces energy recovery
is chosen to be combined with AOPs to treat textile wastewater.
Feature Aerobic MBR Anaerobic MBR
Permeate quality Excellent High
Organic removal High High
Footprint Small Small
Organic loading rates High to moderate High
Biomass retention Total retention Total retention
Sludge production High to moderate Low
Nutrient requirement High Low
Sensitivity to temperature Low Low to moderate
Energy requirement High Low
Energy recovery No Yes
Table 8 Overall parameter of aerobic and anaerobic MBRs (Jegatheesan et al., 2016)
Finally, AOPs combined with anaerobic MBR technology is proposed to design a technically and
economically feasible option for treating textile wastewater and recycling its wastewater for sustainable resources.
Figure 1 depicts the proposed method for treating textile wastewater.

Figure 1 Proposed method for treating textile wastewater

6. Conclusions
Textile wastewater contains high amount of dye compounds and recalcitrant organic pollutants which are
non-biodegradable and toxic. Therefore, it is important that textile wastewater should be treated properly before
being discharge into the environment. Among the various treatments processes currently used, chemical method
is the most effective process for color and COD removal in textile wastewater. AOPs are classified into chemical,
photochemical, sono-chemical, and electrochemical processes. By considering the operational cost and organic
compounds degradation, the most promising AOP is photochemical using ozone as an oxidizing agent.
Meanwhile, biological treatment is the easiest process among other treatments, low cost and high color removal.
Application of physical, chemical, and biological methods individually will not achieve maximum removal for textile
wastewater treatment. Otherwise, in this mini-review was proposed the method that can be used for recycling
textile wastewater by using the combination between AOPs (O 3H2O2/UV) followed by anaerobic MBR. Anaerobic
MBR was selected as hybrid process with AOPs for textile wastewater treatment and water recycling process due

8
 Textile wastewater treatment by hybrid advanced oxidation processes

to its capability for high organic compound and color removal, low footprint, and high quality recyclable treated
water. This hybrid treatment process is a potentially beneficial approach for reusing textile wastewater, for
reducing water consumption and pollutant disposal, as well as for water conservation.

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