An Insight Review on Textile Effluent Treatment Using Nanoparticles

Introduction

At present, one of the most important impacts of rapid industrial growth is

pollution. These industries release their waste or effluent into the water bodies which gets
contaminated .The effluents released from the industries can be classified as Conventional and
Non -Conventional. The conventional effluents comprises of suspended solids, pathogens, fats,
oil and greases. The non-conventional effluent mainly consist of metallic substances like silver,
arsenic, copper, lead, mercury and many more heavy metals. Other effluent like
polychlorinated biphenyls (PCB’s), ammonia, phosphate and toxic herbicides and pesticides are
also released.

Common sources of industrial effluents:

1. Electric power plants :

There is major unit process involved in electric power plants:
Firstly, the fuel materials are transported to the power plants and they are pulverized to
increase the efficiency and stored. Then, the fuel is burnt and the heat produced is sent into
boilers which in turn changes the liquid into steam (Srikanth., 2015).The obtained steam is
allowed to pass through the turbine where the turbine starts to rotate and produces electricity
after which the steam is passed through the condenser which condenses the outlet steam from
the steam turbine and condensed steam is obtained in the form of pure water. The water is
then pumped back to boiler.

Amongst the above mentioned stages, condensation of the steam produces wastewater
effluents. Though wastewater effluent parameters do not exceed the sewer system limit, they
exceed irrigation standards that are of concern. 

Methods to treat the wastewater effluents:

 These are following methods employed for the reduction of waste water effluents produced by
the electric power plants.
 Waste water effluent analyses for the electric power plants:

Parameter Average Maximu Standard sewer Standard irrigation

s m
Temp.(˚C) 29 36   -   -
PH 7.9 9.4 5.5-9.5 6.5-8.4
BOD (mg/l) 13 43 800   -
COD ( mg/l) 28 64 2100
Zn (mg/l) 0.3 6.75 15
Cl(mg/l)  - 711  - 350
FOG(mg/l) 0.5 2.0 50 5
*BOD - Biological Oxygen Demand
COD - Chemical Oxygen Demand
FOG - Fats, Oils and Grease
(*Reference: Viveka Mude et al., 2015)
2. Nuclear Industry:
The Nuclear power plant produces radioactive substances as effluents which are released in
airborne and liquid forms.
Airborne effluents released in nuclear power plants:
Airborne effluents are released mainly due to nuclear fission and activation of gases like
Tritium. Airborne effluent released from nuclear power plant also display significant variability
across time. Both PWR(pressurized water reactor) and BWR(boiler water reactor) releases
airborne effluent(Andrej Trkov et al., 2013). The variability in airborne effluent is due to designs
and operations of radioactive waste management and effluent control systems and analytical
methods used to monitor the effluent released.
Common radio active nucleotides reported in airborne effluents released from nuclear power
plants:
 Category Commonly reported radionuclides
Fusion and activation gases Krypton
Xenon
Argon
Halogens Iodine
Bromine
Particulates Cobalt
Cesium
Chromium
Manganese
Niobium
(*References: Sidebar (2015))
Liquid effluent released:

Liquid radioactive effluents that are released in surface water are monitored prior to authorize
release to the sea. In addition, uncontrolled leaks of liquid radioactive effluents due to fission
activities have resulted in contamination of groundwater. Tritium activity in liquid effluents is
much higher for PWR than BWR. Currently, nuclear plants typically release a few curies of
tritium in liquid effluents due to the mixed fission and activation products. There is a variation
with time of liquid effluent released from the Dresden plant (BWR) located at US and tritium
released in liquid effluents for selected PWR and BWR

Common radioactive nucleotides reported in liquid effluent released in nuclear industry:

Category Commonly reported radionuclides

Mixed fission and activation products Iron
Cobalt
Cesium 
Chromium
Manganese
Zirconium
niobium
Iodine
Tritium Hydrogen(3)
Dissolved and entrained noble gases krypton
Xenon
(*References: VM Efremenkov(2016))
3. Petroleum Industries and Petrochemicals:
Transport fuel processing industries produce both liquid and gaseous pollutants. Gaseous pollutants
are easier to manage compared to liquid pollutants. ETP (Effluent Treatment Plant) can
efficiently treat the liquid pollutants to protect from environmental pollution.The treatment
systems for the effluents produced by the petroleum industries involves removal of coarse
suspended and floating matters, oil, grease, organic solids through biological processes,
colloidal particles and refractory organics.
 Literature on petroleum waste water treatment, parameters investigated and findings:

Pollutant type Parameters Results

investigated
Petroleum refinery COD, BOD, Oil and Identified photo-catalytic degradation as efficient
effluent grease technique
Oil and greasy COD Significant amount of COD(about 85%)reduction
effluent within 10 minutes
Heavy oil produced BOD, COD, TKN, Surface flow constructed wetland can be removed
as effluent oil
Highly saline waste NaCl, turbidity RO is efficient for removing the salt concentration
water and organic matters
Oily waste water COD and oil Photocatalytic decomposition of oily waste water
content by modification of catalyst activity
(*Reference: D Aljuboury(2017))

The above mentioned abatement techniques are used in both petroleum and petrochemical
industries for effluent treatment. The widely used for oil – water separation is practiced in API
(American petroleum institute) to separate oil and grease.

4. Organic chemicals manufacturing industries:

The chemical industry has a great impact on the environment. The wastewater released from this
industry aregenerally highly concentrated with organic and inorganic pollutants which may be
toxic. Most of the effluents released this industry are mutagenic, carcinogenic, and non-
biodegradable. The methods used for the treatment of effluents includes Chemical treatment
(using FeCl3 and lime) and Biological treatment (Activated sludge treatment and Rotating
biological unit).

Characteristics of treated effluent produced by the chemical industry:

Parameters     Raw Effluent treated   %removal

COD (mg O /l)
2 5239 474 90
BOD (mg O /l)
2 2615 277 89
Total organic nitrogen (mg N /l) 181
2   81 56
Total phosphorus (mg P/l) 7.2  3 57
Phenol (mg/l) 0.4 0.02 95
Total suspended solids (mg/l) 608 76 88
(*Reference: FA Nasr(2011))
5. Iron and steel industry:
In an integrated iron and steel industry, wastewater generated from coke oven by-product plant is
considered to be the most polluting. This wastewater contains toxic chemicals like phenol,
cyanide, and ammonia which are harmful to the receiving water bodies.

Impact of steel industry on water bodies:

 The major harmful effects of the untreated waste water of steel industry if discharged into the
receiving water bodies are: toxicity to aquatic life, reduction of D.O, silting due to suspended
solids. Toxicity to aquatic life is due to the ammonia and phenol released in the effluent which
increases the PH of the water. Due to the discharge of biodegradable organic substances into
the water bodies, the soil and bacteria use the organic matter as source of carbon and DO
(dissolved oxygen) in the water for required for the respiration of aquatic organism decreases.
Entrapped oil and grease from the effluent lead to the formation of oil slicks and poor
aesthetics.

Treatment:

In the existing plants, COBP(coke oven by product) wastewater is treated by biochemical

oxidation of cyanide, ammonia and phenol. These effluent treatment plants are commonly
known as bio chemical oxidized or BOD plants. Different oxidation techniques had been
implemented in order to reduce pollution, mainly caused by the organic compounds.

Toxic effects caused by various pollutants generated from effluent of iron and steel plant:

Class of Toxic effect   Disinfection

pollutants
Heavy metals Poisonous interference to enzyme Blood and cardiovascular,
systems and metabolism of body reproductive and urinary system

Aromatic PAH have different type of toxic action, Non-polar narcosis, photo toxicity
compounds depending on the compound results in mutagenicity and
carcinogenecity
Surfactants Enhance the bio availability and stimulate Negative impact on the survival of
the biodegradation  heterotrophic nano flagellates and
ciliates
Cyanides Dynamic effects depends on the dose, Lethal toxicity after inhalation of
route and speed of administration hydrogen cyanide gas affects many
including the physical condition of functions in the body
recipient
Flourides Intake of 20-40 mg/day can inhibit the Osteoporosis and arthritis, cancer,
important enzyme phosphatase infertility brain damage.
(*Reference: P Das(2014))
6. Food industry:
The waste water released from the food industry cause pollution due to its high COD and BOD
content. Compared to other industries, food industry requires great amount of water, since it is
used throughout most of plant operations. The waste water from these industries shows large
variation in BOD/COD, total solids and suspended solids.  This is due to the different additives
used for different food products.
                       Chocolate industry is among the most polluting of the food industries with regards to its
large water consumption.
 Treatment methods for the effluents produced by the food industry:

Treatment methods Components Results

Dissolved air flotation Aeration tank, Reduction of both free oil and grease and
Filter press suspended particles
Biological treatment unit Aeration tank, Effect of oil and grease available in the
Anaerobic emulsion form can be reduced
fermentation tank,
Sludge preparation
tank,
Thickener
Physical and chemical Equalization tank, Operation is not fully automatic but
treatments in tanks Mixing tank, reduces the toxic pollutants
Chemical dosing
pump,
Centrifuge
(*Reference: NA Noukeu(2018))
6. Leather industry 
       Leather industry is one of the fastest growing and most polluting industries globally. The leather
processing is responsible for the unfavourable conditions of environment. The most commonly
used animals in the leather processing are sheep, cattle and pigs. The leather obtained by
processing is used for various purposes like shoes, cloth (textile), carry bags and many more.
For this, huge amount of raw materials are collected and they are subjected to chemicals for
obtaining the complete finished product (References: A Lashini et al., 2017)
      Generally the skin of the animals is mainly composed of water, protein and fatty materials.
Every leather factory must undergo three stages such as Preparatory, Tanning and Crusting.
Preparatory phase/Pre tanning process:

   It is the phase where the skin is prepared for tanning process. In this phase, unwanted raw skin and
hairs are removed .This process involves Soaking, Unhairing, Liming, De -liming and Bathing

Tanning process:

 Tanning is the largest process in the leather manufacturing industry. It is the process of converting
unstable raw materials to leather with adequate strength properties and resistance to
biological and physical attacking agents(Mirulanini V et al.,2017). In this a tanning agent is
introduced into the skin. The commonly used tanning agent is chromium (Cr(III))  salt which is
added after pickling(making the fibre of hides receptive to tanning) which increases the P H of
the hide and to obtain leather of higher thermal and bacterial resistance . The chromium
tanned leather contains about 2%-3% of dry weight of chromium salts .It is also used to
improve color, appearance and look of the processed leather. About 90% of leather
manufacturing industry uses chromium. 

Wet tanning/Post-Tanning:
The wet processing includes re-tanning with chromium and also addition of some dye and fats for
improving the smoothness and color and after several process of drying and re-tanning ,the
product is available in the form of crusts .The crusts obtained is subjected to undergo the
finishing process(Tapan Biswas et al., 2017) .Finishing process is undergone to obtain more
softer and clean leather as product. The finished end product has about 65%-80% of the dry
weight of chemicals used.

Usage of water in leather manufacturing

Water is one of the important element in every industries. In leather industry water is used mainly in the
tanning process .In addition to the usage of water in every individual steps water is also used in
vacuum dryer. The minimum amount of water required for good housekeeping is 3-5m 3/ft.

Water consumed in every individual steps:

Operation Water consumed(m3/ft)

Soaking 7-9
Liming 9-15
De-liming and 7-11
bathing
Tanning 3-5
Post Tanning 7-13
Finishing 1-4
(*References: Swetha singh(2016))
Wastewater Treatment

 The wastewater from tannery industry mainly classified on the basis of the composition of
Biochemical Oxygen Demand(BOD),Chemical Oxygen Demand(COD),suspended solids(SS) and
Total Dissolved Solids(TDS),Chromium and sulfides etc. Treatment such as primary, secondary
and tertiary are necessary to remove the chemicals present in the wastewater

Primary treatment:

The primary treatment includes elimination of clogging by coarse particles, providing raw
material in consistent manner, decreasing BOD and COD level to reduce the cost of biological
treatment, reduction of levels of chromium and sulphides(A Lahsini et al., 2017).

The steps involved in primary treatment are: Screening, Pumping, Fine screening, Equalisation
and sulphide oxidation, Chemical treatment, Settling, Sludge dewatering.

Screening: Screening is mainly done to remove large molecules, grits and floating
materials. Removal of large molecules is done by the bar screening which have the opening size
of about 10mmto 35mm and the bar screens are kept in the angle 0 to 30 degrees vertically.
The grits and floating materials are removed by non-aerated floating chambers which is placed
horizontally.
Pumping: Pumping is used to transfer the effluents depending upon the usage of pumps, submersible
pumps are used for medium scale and screw (Archimides) pumps are used for large scale.

Fine screening: Fine screening is used to reduce the fine suspended solids. Usually a rotary
drum screen with outer and inner flow is used.

Equalization and Sulphide oxidation: This process is mainly done to homogenize the effluent
and to eliminate sulphide by catalytic oxidation.

Chemical  Treatment: Chemicals are added in order to improve and accelerate the settling of
suspended solids, especially fine and colloidal particles. The commonly used chemicals are
aluminiumsulphate(Al (SO ) .18H O),Iron sulphate(FeSO 7H O)
2 4 3 2 4. 2

Settling: The main objective of this method is to remove the suspended solids,waxes,
minerals(remaining from grit and chamber) are also separated in this procedure. 

Effluent

Screening Coagulation Fine

cloth Feed tank

Large sludge tilter

pump
particles

fine particles
Pure water

Secondary Treatment (Biological Treatment)

This treatment is used to remove the organic matters namely BOD&COD and other substances that
are still present in the effluent after primary treatment. This process can be done by using both
aerobic and anaerobic micro-organism. The most commonly used is the aerobic micro organism
is Bacillus species which is exceptional in the hot climatic conditions where anaerobic micro
organisms are used (G Durai et al., 2005). In aerobic respiration, the most widely used is the
activated sludge with extra aeration system, which uses the metabolism of the micro organisms
to remove substances that causes oxygen demand.

PARAMETER     PHYSICAL AND CHEMICAL         BIOLOGICAL 

S REDUCTION % APPROX.VALUE  REDUCTION % APPROX.VALUE
       mg/l              mg/l
SS       80-90   300-600       95-98       20-50
BOD       50-65     750-1500     97-99       20-30
COD       50-65     1500-3000       87-93     250-400
TKN       40-50     250-300     60-75       100-200
Cr       92-97       5-10       99-99.5         <1
TDS, mainly Cl                                               NO REDUCTION!
-

*SS – suspended solids

TKN – total kjeldal nitrogen
TDS – total dissolved solids
(*Reference: NV Gupta,2019)
  Tertiary Treatment
        In some cases, the final effluent does not meet the needed discharged limits. Mostly
tertiary treatment are done before the release of the effluent, this happens due to the
presence of abundance amount of BOD&COD in the effluent. This is done by expensive
treatments such as mineralization of organic compounds by oxidation of H O in the presence of
2 2

ferrous sulphate(R. Belaabed,2015). Ozonation is also done not to kill the microbes present and
to remove the residual part of BOD.

vii. Paper and Pulp Industry:

Paper and pulp has a huge impact on our everyday life. Pulps are used for paper and board
production. The paper and pulp industries produces huge quantities of biomass .Tow is
important for the determination of pulp yield and the conditions to be used for the digestion
are cellulose content and the amount of lignin and its structure(Hubbe et al., 2016).

 The production of pulp and paper involves many steps such as Debarking, Chipping, Pulping,
Bleaching, Paper manufacture from pulp and paper waste

DEBARKING: Drum debarking is the most common way of eliminating bark in the paper and
pulp industry.

CHIPPING:The chippers are large rotating disc equipped with chopping knives. The chips are
either stored or processed in stockpiles.

PULPING:Pulp, the raw material for paper making process, is a lingo-cellulosic fibrous material,
which is produced from the separation of the cellulosic fibers in wood, fiber crops and waste
paper. There are three types of pulping namely Mechanical, Chemical and Semi-chemical
pulping.

Type Variant Description End-use

Mechanical Stone Ground Mechanical grinding of the wood Used in the newsprint
Pulp wood Pulp into short fibers and wood containing
paper, such as
lightweight coated
papers
Thermo- The wood particles are softened Mainly used in the
mechanical by the steam before entering the super calenderer papers
Pulp(TMP) pressurized refiner
Semi- Semi-Chemical Produced in the same way as of Used in the tissue
Chemical Pulp TMP ,but the wooden particles are manufacture. Some
Pulp made to undergo the chemical CTMP is also used for
treatment before entering the writing and printing
refiner grades
Chemical  Sulphite Pulp Produced by cooking wood chips Varies from newsprint,
 Pulp in the pressure vessel in the printing and writing
presence of bisulphateliquor. papers
Sulphate/Kraft Pulp is produced by cooking the Pulp used for the
Pulp chips in the pressure vessel in the graphic papers, tissues
presence of sodium hydroxide and carton boards
liquor.
(*Reference: MN Cabrera., 2015)
BLEACHING:Raw pulp contains an appreciable amount of lignin and other discoloration, it must
be bleached to produce light colored or white papers preferred for many products. Chemicals
used in the bleaching process include sodium bisulfate, sodium or zinc hydro sulphite, calcium
or sodium hypochlorite or sodium peroxide, and the sulfur dioxide-borol process.

PAPERMAKING PROCESS: Bleached or unbleached pulp may be further refined to cut into
fibers. Water is added to the pulp slurry to make a thin mixture normally containing less than 1
percent of fiber. The pulp is screened in the centrifuge screening before they are sent into the
wet-end of the paper making process.

Wastewater Treatment

In the modern plant four types of effluent can be estimated that condensates from cooking and
evaporation, washing and draining, preparation of wood and pressing, bleaching.

 Amount of wastes present in the effluents from the industry

PROCESS YIELD  WASTEWATER BOD TSS COD Pt-Cd color

VOLUME Kg/l Kg/l Kg/l Kg
TMP 94-95 13-22 50-80
Mechanical 95-97 15-25 8.5-14 10-30 20-55
Bi sulphite 40-90 10-30
-Unbleached 60 40-60 25-50 10-110 75-150
-bleached 50 50-100 20-60 20-150 35-120
Kraft 55 20-80 1-20 0.2-15 7-50 20-50
-Unbleached
-Bleached 45 30-110 0.2-40 0.2-10 4-90 100240
normally
-OZP Bleaching 45 1-20 40-80
CTMP 92-94 17-30 60-100
-Bleached 91-93 10-30 20-40 10-30 80-130
-De-inked  15-30 15-20 20-40
(*Reference: Devendra Singh, 2017)
TEXTILE INDUSTRY 

Solid and water effluents produced in textile industry:

PROCESS WATER  EFFLUENTS SOLID    EFFLUENTS

 Fiber preparation   No water effluents 1.Fiber waste
2.Packaging waste
Yarn spinning   No water effluents Cleaning and packaging
waste(sized yarn)
Sizing 1.BOD(biochemical oxygen demand) 1.Fibre lint
 2.COD(chemical oxygen demand) 2.Unused starch-based sizes
Weaving   No water effluents Off – spec fabrics
Knitting   No water effluents   Fabric scraps
Tufting    No water effluents   Off – spec fabrics and fabric
scraps
De-sizing  1.Lubricants 1.Fibre lint
2.Anti –static compounds 2.Yarn waste
Scouring  Disinfectant, insecticide, residues, NaOH,   No solid effluents
spent solvents
Bleaching H O , Stabilizers
2 2 No solid effluents
Singeing Exhaust gases(small amount) No solid effluents
Mercerizing NaOH(solvent)   No solid effluents
Heat setting Volatalisation  of spin finish agents No solid effluents
Dyeing Metals, salt, surfactant, spent solvents No solid effluents
Printing and Solvent, acetic acid, contaminants   Trimmings
finishing

ENVIRONMENTAL IMPACTS OF TEXTILE EFFLUENTS:

1. Textile dyeing:

During  textile dyeing ,  poisonous chemicals  such as Arsenic, Formaldehyde,  Lead and
Mercury are used which  are harmful to Macrophytes which hardly  survives for two days
on textile effluent.

2. Dyeing  Process:

During  dyeing process,  10-15% of dyes are  released into the environment  making the
effluent highly colored  and aesthetically unpleasant(AE Ghaly.,2014).  Dyes  remain  in
environment  for longer time  because it has high  thermal and photo stability(absorption
and reflection of sunlight  entering the water) to resist bio degradation.

3. Finishing  process:

During  finishing  process, there  is a release of  lubricating oils, plasticizers,  acid vapours,
boiler exhaust that  results in the sludge formation in the tanks  containing toxic
compounds and metals(AE Ghalu.,2014).  Coating materials also causes air pollution.

4. Cotton:
Cotton  is bad for  environment because  it uses huge amount  of toxic and
agrochemicals(pesticides). Non- organic  cotton is genetically modified and it is treated
with  fungicides and insecticides.

Methods of treatment of  textile effluents:

Treatment  Effluent  Advantage Disadvantage

Methodology treated
Precipitation  and coagulation Arsenic, fluoride, Short  detention  Agglomerates 
phosphorous time separation and 
treatment
Coagulation  Alum,   Feasible    Increases  sludge
polyaluminium production
chloride,  iron
salts
Fenton  process BOD,  COD Applied  for both    Expensive
soluble and
insoluble colored 
contaminants
Ozonation    Nitronium  ions Used  for azo  dye Not  suitable  for
removal dispersed  dye
Oxidation  with NaCl Phenol  and Requires  low Release  of
ferric  salt temperature aromatic  amines
Adsorption with solid  Olive mill Good removal  Cost  intensive 
adsorbents(activated carbon, wastewater, efficiency of regeneration 
peat, silica gels, coal ashes) titanium oxide variety  of dyes process

Emerging technologies like All  kinds  of solid  Recovery  and Purification  is

Membrane filtration, and liquid  reuse  of tedious
Photocatalysis,  Sonication and effluent chemicals
Enzymatic treatments
(*Reference: PDS Vineta., 2015)
APPLICATIONS   OF NANOTECHNOLOGY   IN TEXTILE EFFLUENTS:

SYNTHESIS OF NANOPARTICLES:

1. By  laser  absorption:

The  absorption  of laser beam  with nanoparticles  is the effective factor  of the laser
ablation process  at high laser fluency to prepare  the nanoparticles in an aqueous
solution.  When the prepared nanoparticles have not high  mobility in liquid, they are
aggregated near the  target. Laser ablation is a simple method for fabricating  the metal
nanoparticles without surfactant or chemical addition(Amir Reza et al., 2018)
 When  the laser  beam is focused  on the surface of  the solid target material  in the
ambient media(gas or liquid) , the  temperature of the irradiated spot rapidly  increases,
vaporizing the target material. Laser  ablation in liquid is employed to confine the
plasma  plume in a small region to directly disperse the nanoparticles  in the liquid phase.

    
liquid
Laser beam

Lens

Metal
controller
plate

2. Micro emulsion:

Nanoparticle  synthesis with  co precipitation is  an easy technique, resulting  in a wide

ranging size of nanoparticle  synthesis. Magnetite nanoparticles are produced  by a mixture
of nano emulsion consisting of iron  source and sodium hydroxide. Acetone lyses is used
for  the removal of nanoparticles from the surfactant and washed  with ethanol(MA Malik.,
2018). In this technique, surfactant molecules are dissolved in organic solvents to form
spheroidal aggregates that are known as reverse micelles. If the medium is free of water then
aggregates are very small, while the presence of water makes large surfactant aggregates.
Water is readily solubilized in the polar core and form “water pool” contents. These water pool
contents are characterized by water-surfactant molar ratio. The aggregates containing a small
amount of water are usually called reverse micelleswhereas aggregates corresponding to
droplets containing a large amount of water molecules are called Microemulsions. The nano
droplets obtained in this method can be used as nanoreactors to carry out the chemical
reactions(SF Chin., 2012).

In order to produce the nanoparticles, two micro emulsions carrying the appropriate reactants
are mixed. The Brownian motion of the micelles leads to intermicellarcollisions and energetic
collisions lead to a mixing of micellar contents (B Richard., 2017). The chemical reaction starts
when there are fusion-fission event between the droplets as a perquisite for the mixing of the
reactants. After the chemical reaction has taken place at the nanodroplets, critical number of
molecules is produced, which results in the formation of further more growth of nanoparticles.
 Reverse micelle emulsion

Catalyst pellet

Aqeous solution
of metal salt

3. Chemical vapor deposition

It is a chemical process used to produce high purity, high performance solid materials. In a typical CVD
process, a wafer (substrate) is exposed to one or more volatile precursors, which react or
decompose on the substrate surface to produce the desired deposit. The volatile by-products
are also produced, which are removed by gas flow through the reaction chamber. In this
process, thin films or coatings are produced by the dissociation and chemical reactions of
gaseous reactants in an activated (heat, light, plasma) environment. The resulting solid material
is in the form of thin film, powder or single crystal (J. RandallCreighton.,2014). A characteristic
feature of CVD technique is that it enables the production of coatings of uniform thickness and
properties with a low porosity even on substrates of complicated shape.

Different types of Chemical vapor deposition applied for the synthesis of Nanoparticles:

TYPE DESCRIPTION
Atmospheric pressure CVD Processes at atmospheric pressure
Low – pressure CVD Processes at sub atmospheric pressure
Ultra high vacuum CVD Processes at a very low pressure
Aerosol – assisted CVD Precursors are transported to the substrate by
means of liquid/gas aerosol, which can be
generated ultrasonically
Direct liquid injection CVD Liquid solutions are injected in a vaporization
 chamber towards injectors.
Microwave plasma assisted CVD Utilizesa plasma to enhance chemical reaction
rates of precursors.
Atomic layer CVD Deposits successive layers of different
substances to produce crystalline films
Hot wire CVD Uses a hot filament to chemically decompose
the source gases.
Metal – organic CVD Based on metal – organic precursors.
Rapid thermal CVD Uses heating lamps to rapidly heat the wafer
substrate.
(*Reference: Henrik Pederson et al., 2014)

Radiation

heating

Components

Mixing control

Pump

In this method, the precursor is converted to nanoparticles and this technique is used to
synthesize ceramic nanopowders. This method is mainly used for fabrication of oxide, nitride,
and carbide nanopowders and also carbon nanotube. Laser – induced chemical vapor
deposition (CVD) is the recently developed method to prepare amorphous or crystalline
nanopowderswith controllable particle size and homogeneous size distribution. A technique
named as Inert Gas Condensation has been developed to synthesize nano sized TiO 2 powders,
involving formation of ultrafine Ti particles.
Partially pyrolyzed metal
alkyls in gas stream

Stagnant boundary layer

substrate

Methods for the production  of nanoparticles  for textile fibres:

 Attritor  milling and  air – jet milling

 Spray  milling  and agitation  bead milling
 Freeze  drying
 Nano spray drying
Attritor milling and air jet milling:
Fibroin protein derived from silk fibres has been extensively used for the advanced
biomaterial applications. In this method, the silk cocoons were degummed and the extracted
silk fibreswere chopped into snippets prior to attritor and jet milling. There are two types of
attritor milling namely, Dry and Dry – wet milling in which wet process is preferred as it causes
less color change. Ultrafine silk powder with a volume based particle size of around 700nm
could be prepared in the following sequence:
Chopping wet attritor milling spray drying air
jet milling

A volume based particle size analysis better is a better approach to ascertain the relative
effectiveness of the milling techniques, particularly for assessing scale – up production. Thus,
pre-treatments are necessary for the production of fine undegradednano powder.
Spray milling and agitation bead milling:
This technique involves following steps:
  Wetting of particle surfaces in a liquid medium.
 Mechanical size reduction of solid particles that are either flocculated, agglomerated,
aggregated or crystalline.
 Stabilizing the newly reduced nano particles in the dispersion by preventing re –
agglomeration using surfactants or dispersants.

Anano-particle dispersion is a homogeneous distribution of materials in a liquid phase. High-

quality dispersions typically possess high stability with a long shelf-life, resist sedimentation.
In this method, a very large no. of nano particles could be crowded together to perform a
superior grinding/milling of product. This process is done primarily by exhibiting shear
force on the solids of the slurry following through the spacers in the beads as the solid
particle in the slurry and the beads move each other at different velocities. The circulating
cooling systemeffectively maintains the optimal operating temperature. Feed pump is
equipped with inverter controlled transmission motor to achieve the best material feeding.

Freeze drying:

This method also known as lyophilization method involves removing water from a frozen
sample by sublimation and desorption under vacuum condition. Freeze drying of nanoparticles
helps to preserve a solution’s homogeneous properties and to achieve targeted particle size. It is a
good technique to improve the long-term stability of colloidal nanoparticles. In this process, the
liquid suspension is cooled, and ice crystals of pure water forms. A freeze-dried nanoparticle
possess certain characteristics such as:
 Preservation of primary physical and chemical characteristics of the product such as
particle size, short reconstitution time etc.
 Acceptable relative humidity
 Long-term stability
This technique involves following steps:
 Formulation
 Freeze-drying process
 Storage

Components used in the production of nanoparticles in freeze drying method:

Type Substance
Bulking agents Hydroxy ethyl starch, glycine
Buffers Phosphate, citrate
Stabilizers Sucrose, lactose, glucose
Tonicity adjusters Mannitol, glycerol
Temperature modifiers Dextran, PEG
    Nano spray drying:

It is a granulation technique which can be used for the production of free flowing low dusty granules
from the suspension of nanoparticles. Spray dried granules are well suited for subsequent
processing of final products where the superior properties given by the nanoparticles are
retained. Nano spray dryers are used in spray drying to create particles in the nanometer
range.

Drying gas flow

Drying chamber

filter

Grounded
electrode

In this technique, the drying gas enters the system via heater. The spray head sprays the fine
droplets with a narrow size distribution into the drying chamber. The droplets dry and become
solid particles. These solid particles are separated in the electrostatic particle collector. The
exhaust gas is filtered and sent to a fume hood. The inlet temperature is controlled by a
temperature sensor. The contact between the hot inlet air stream and spray causes evaporation of
solvent.

APPLICATIONS OF NANOTECHNOLOGY IN TEXTILE EFFLUENTS 

  Decolourisation  of dye:
Nickel nanoparticles were synthesized and used to decolorize dye effluent. To confirm the
attachment  of degraded products of dye on nanoparticles,  FT-IR analysis is done. About
98% color removal  with simultaneous reduction in chemical oxygen demand(COD)  was
achieved. Reactive Blue 21 was taken as reference dye,  and polyvinyl pyrrolidone(PVP)
was used as a stabilizer to prevent  agglomeration of nanoparticles(S batool.,2014).
                            Metal  nanoparticles  are also employed  for decolorization of  the colored effluent.
These  particles show tendency to aggregate  and thus lower the activity.
Examples of different dyes in textile effluents that are removed by nanoparticles:

Dyes Examples Toxicity

Acid sunset yellow, methyl orange Carcinogenic
Cationic Methylene blue, rhodamine Carcinogenic
-6G
Disperse Disperse orange 3, disperse Allergic (skin)
red
Direct Congo red, direct red 23 Bladder cancer
Reactive Reactive red 120, reactive red Dermatitis
198
Nano sized metal or metal – oxide based materials or inorganic nanomaterials are used broadly
for the removal of dyes which includes nanozerovalent iron (109), nanozerovalent zinc (110),
magnetic Fe2O3 (111), magnesium oxide (MgO) (112), titanium dioxide (113) , zinc oxide (114),
provide high surface area and specific affinity. For metal oxides, these materials have a minimal
environmental impact, low solubility. These particles have a high efficiency in eliminating a
variety of pollutants, such as nitrates, organochlorine pesticides, heavy metals and dyes.
For example, humic acid is used to coat on Fe3O4 nanoparticles to temoveRhodamine B. In this case,
humic acid prevented Fe3O4 nanoparticles from being oxidized and enhanced its stability.
Nano sized alkaline earth metal oxides, in particular magnesium oxide has been extensively
used as a destructive adsorbent for the removal of many toxic chemicals due to their high
surface reactivity and adsorption capacity.

Dyes removal by different nanomaterials:

Adsorbents Adsorbate Efficiency

Fe3O4nanomaterials aeridine orange 0.056 (mol/g)
HA – Fe3O4 Comassie brilliant blue R – 0.082 (mol/g)
250, congo red
MgO nanoparticles Reactive black 5 500 mg/g
Rice straw charcoal/ Reactive blue 221 27.78 mg/g
MgOnanocomposite
Magnetite/ reduced Rhodamine B 16.2 mg/g
grapheme oxide
MgOnanoflakes Malachite green and congo 97.42 %
 red

 Remediation  of the waste  water using Nanoadsorbents:

Nano-particles  are used as adsorbent  for the removal of heavy  metals are non-toxic and have 
high adsorption capacity and to  adsorb pollutants in less concentration(ppb),  adsorbed
pollutants that can be easily removed  from adsorbent surface and can be recycled for
numerous  times. Nano – catalysts are employed for degradation of pollutantsin wastewater.
Fenton based catalysts are used for improving the  chemical oxidation of organic
pollutants and catalysts having anti -microbial  properties.
                    The  smaller  size of the  nanoparticles increases  the surface area which enhances  the
chemical activity and adsorption  capacity of nanoparticles for the adsorption  of metals
on their surface. The frequently used  nano-particles for the adsorption of heavy metals
are  activated  carbon,  carbon  nanotubes,  manganese oxide,  graphene, zinc oxide,  titanium
oxide and ferric  oxides.

 Oxide-based  nano-particles:
Oxide – based nano particles are inorganic nano-particles which are usually prepared by non-metals
and metals. These particles are extensively used for hazardous pollutants removal from
wastewater which includes: titanium oxides, dendrimerscomposites,zinc oxides, magnesium
oxide, manganese oxide and ferric oxides. Application  of oxide based  Nanoparticles for  the
removal of heavy  metals from the aqueous  systems is developed as high  efficient and
cost effective nanoadsorbent.  Surface modification approach enhanced their stability and
efficiency in water.Oxide – based nano-particles are characterized by high BET surface area,
minimum environmental impacts, less solubility, and no secondary pollutants.
 Iron- based  nano particles:
Iron- based  nanoparticles, more  specifically magnetite(Fe O )  and  magnetite(Fe O )  are  the most 
3 4 2 3

extensively  used magnetic  nanoparticles for  water treatment in  textile industry due  to
their adequate magnetic  properties, low cost, chemical  inertness and low toxicity. Iron 
oxides nanoparticles have shown prominent  result for decontamination of arsenic from 
the water. So they could become cost-effective  materials for decontamination of arsenic
from the  water. The natural occurrence of iron and its simple synthesis process make ferric
oxide a low cost material for the adsorption of metals. It is an ecofriendly material and can be
used directly to a contaminated environment with less chance of secondary contamination.
Factors affecting the adsorption of different heavy metals on Fe 2O3nano-particles depend on
pH, temperature, adsorbent dose and incubation time. Modification of nano-adsorbants show
high affinity for the removal of different pollutants such as Cr3+, Co2+, Ni2+, Cu2+, Cd2+, Pb2+
simultaneously from wastewater.
 Manganese-oxide  based nanoparticles:
Manganese  oxide nanoparticles  have been used as adsorbents  and catalytic materials.
Degradation  of dissolved organic contaminants through  oxidation by Mn-oxide surfaces
has been employed  for large scale. Application of manganese oxide have  shown
prominent results in columns for the removal of  chemicals such as diclofenac and
estradiols via biotic and  abiotic mechanisms. These nanoparticles show high EBT surface area
 and polymorphic structure. It has been used for the removal of various heavy metals such as
arsenic from wastewater. Most frequently used modified MnO include nanoporous/nanotunnel
manganese oxides and hydrous manganese oxide, which is prepared by adding MnSO4.H2O into
NaClO Solution. Adsorption of various heavy metals such as Pb(II), Cd(II) and Zn(II) is usually
happened due to the inner-sphere formation mechanism that can be defined by ion-exchange
process. Adsorption of divalent metal metals on the surface of manganese oxide occurs in two
steps:
 Metal ions adsorb on the external surface
 Intraparticle diffusion
 Zinc-oxide  based nanoparticles:
zinc  oxide nanoparticles  are used for the development  of antimicrobial cotton fabrics.  The ZnO
nanoparticles were prepared  by wet chemical method and were directly  applied on to
the 100% cotton woven fabric  using pad-dry-cure method. It is used for the 
functionalization of the textile substrate. The use  of nanoparticles of zinc in textile
industry has been  as a viable solution to stop infectious diseases due to  the
antimicrobial properties. In addition to these, They also  posses excellent UV- blocking
properties. Zinc oxide has a porous nanostructure with high EBT surface area for the adsorption
of heavy metals. Nano assemblies, nano plates, microspheres with nano-sheets and hierarchical
ZnOnano-rods are widely used as nano-adsorbentt for the removal of heavy metals from waste
water.

 Magnesium oxide (MgO) nano-particles:

Magnesium oxide (MgO) is used for the removal of different kinds of heavy metals from
contaminated water that is released from textile industry. MgO microsphere has novel structure,
which can improve the adsorption affinity for the removal of heavy metals from the textile
effluents. To increase the adsorption capacity of MgO, different types of modification were
carried out in nano-particle morphology which includes nanorods, nanobelts, fishbone fractal
nanostructures induced, nanowires, nanotubes, and other three-dimensional entities.

 Carbon nanotubes:
Carbon nanotubes have the potential to remove heavy metals and variety of organic
contaminants from wastewater released from textile industry through adsorption. Modified
magnetic CNT have high dispersion ability and can be easily removed from wastewater or used
medium by using magnet. Surface modification of CNT increases its overall adsorption activity.
Acid treatment of CNTs was carried out by using different kinds os acids, which include HNO3,
KMnO4, H2O2, H2SO4 and HCl(N Saifuddin., 2012). Acid treatment removes the impurities
present on the surface of CNTs. Moreover, it also introduces new functional groups on the
surface of CNTs, which increases its adsorption capacity from wastewater. In addition, oxygen-
containing group can also be introduced by microwave-excited surface wave plasma.
Grafting functional molecules/groups on the surface of CNTs is another
way to improve their surface characteristics. It can be carried out in different ways such as
plasma technique, chemical modification and microwave techniques. However among these
techniques, plasma technique is one of the best method due to less energy demand and
environmental friendly process(IY Jeon., 2014). Moreover, CNTs modified with metal/metal
oxide such as MnO2, Al2O3 and iron oxide shows promising results for heavy metals removal
from wastewater.

 Graphene based nano-adsorbents:

Graphene is one of the allotropy of carbon having special features that make it highly favorable
for several environmental applications. Graphene-oxide (GO) is a carbon nano-material that
possess a two-dimensional structure which is produced by the oxidation of graphite layer via
chemical method. The most common method for the synthesis of grapheme-oxide is Hummers
method in which, hydrophilic groups were introduced in GO which requires special oxidation
process(M Kumar.,2018). The presence of these hydroxyl and carboxyl groups as functional
group in GO increases the adsorption of heavy metals from the contaminated water. GO as
adsorbent for the removal of heavy metals from the effluents is getting more attention due to its
high surface area, mechanical strength, light weight, flexibility and chemical stability. GO
possess two main features when compared to other nano-materials such as CNTs;
i. A single layer of GO has two dimensional basal planes available for the
maximum adsorption of heavy metals.
ii. It possess a simple synthesis process, which can be carried out by
chemical exofoliation (application of a caustic chemical or acid such as
alpha hydroxyl acid) of graphite without any metallic catalyst and
complicated instrument.
Moreover, GO did not require any further acid treatment to enhance its adsorption capacity as it
already contains hydrophilic functional group. Graphene and its other composite show a very
high efficiency for the removal of heavy metals from wastewater.

NANO-CATALYSTS
The nano-catalysts, especially those of inorganic materials such as semiconductors and
metal oxides have great application in the treatment of effluents produced by the textile effluents.
Various kind of such as nano-catalysts are employed for effluent treatment such as
photocatalysts, electrocatalysts, Fenton based catalysts for improving chemical oxidation of
organic pollutants and antimicrobial actions.

 Nano-materials as photocatalysts:
Nanoparticles photocatalytic reactions are based on interaction of light energy with metallic
nano-particles and are of great advantage due to their broad and high photocatalytic activities for
various pollutants. Usually these photocatalysts are comprised of semiconductor metals that can
degrade variety of persistent organic pollutants in textile effluents such as dyes, detergents,
pesticides and volatile organic compound. Semiconductor nano-catalysts are also highly
effective for degradation of halogenated and non-halogenated organic compounds, PCPPs and
also heavy metals in specific condition. The simple mechanism of the working of photocatalysis
is based on the photoexitation of electron in the catalyst. The hydroxyl radicals present in these
catalysts oxidize the organic pollutants into water and degradation products.
Among the various nanophotocatalysts, TiO2 is one of the most widely used
photocatalyst due to its high reactivity under ultra violet light and chemical
stability. The efficiency of this catalyst depends upon band gap energy, particle
size, dose, pollutant concentration and pH.CdSnano-particles have been used
extensively for the treatment of industrial dyes in wastewater.
  Nano-materials as electro-catalysts:
The use of nano-material as electrocatalystimproves the performance of fuel cell by achieving
larger surface area and uniform distribution of catalyst in the reaction media. The nano-materials
such as pristine multi-walled carbon nanotubes (pMWCNT), amine-modified MWCNT,
carboxylated MWCNT, hydroxyl-modified pristine multi-walled carbon nanotubes carboxylated
grapheme and XC72 carbon black have high potential of eradicating heavy metals from the
textile effluents(DK Baer.,2013). It was found that the hybrid electro-catalyst has smaller particle
size and better dispersion, which shows high catalytic reduction of modern pollutant 4-
nitrophenol due to efficient electrocatalysis of dioxygen.

 Nano-material based fenton catalyst:

Oxidation of organic pollutants by fenton’s reaction has been widely applied in effluent
treatment. The nano-ferrits with controlled crystalline size, distribution and chemical structure
can be obtained through sol-gel and auto combustion method. The presence of metals such as Ni,
Zn, Co, Cu in these nano-materials modifies the stability and redox properties of ferrites, which
further increases the catalytic efficiency. Magnetically separable nano-particles of iron oxide can
be used as Fenton catalyst for the removal of several types of pollutants. This indicates that these
nano-catalysts have stability towards uncontrolled oxidation of pollutant and organic
intermediate products.

Role of nano-catalysts for oxidation of pollutants:

In textile effluent treatment, nano-material catalyst can be used in chemical
oxidation of organic pollutants. Nano-particles developed from noble metals such as Au, Pt and
Pd have efficient catalytic potential for degradation of variety of organic and inorganic
contaminants in the effluent. Palladium could provide selective removal of pollutants like chloro
hydrocarbons from the wastewater effluent. The synthesized Pd based nano-catalyst (Pd/Fe3O4)
shows high hydro de -chlorination and easy recovery of nano-catalyst through magnetic
separation from wastewater.

NANO-MEMBRANES
Among the current advanced textile effluent treatment techniques, membrane filteration
technology fabricated by nano-materials is one of the most effective strategies. This technique is
highly economical, efficient and simple in design when compared to other treatment techniques.
Beside particle separation from wastewater, nano-membrane plays a vital role in the chemical
decomposition of organic foulants separation. The composition of these types of membranes are
one-dimensional nano-materials such as nanotubes, nanoribbons and nanofibers. For selective
filteration, a membrane fabricated with carbonaceous nanofibers are used for efficient removal of
heavy metals under high pressure(FL Heale., 2018). In addition, the capturing potential of nano-
particles and other small molecules can be enhanced by interconnected NPs and negatively
charged bodies on macroscopic disk-like titanate-nanoribbon membrane.

 Electrospunnano-fiber membranes
This technique includes less energy consumption, less expensive and lighter process as compared
to the existing conventional techniques. Nano-fibers had been applied in textile effluent
treatment containing heavy metals, particulate microbes and salts. The ultimate goal of this
technique is to decrease the COD, ammonia and suspended solids from the wastewater. The
electrospunnanofibrous membrane prepared from polyvinylidene fluoride were used for
separation of particles from wastewater and achieved up to 90% of micro-particles rejection.
These membranes possess potential application in pretreatment of textile effluents prior to
reverse osmosis or ultra-filteration step in wastewater treatment(B Behzodi., 2018). The
electrospun membranes have also been effective in removal of toxic heavy metals such as nickel,
cadmium, copper and chromium. In case of removal of salts from the water in desalination
process in the textile effluent treatment, the use of nano-fiber membrane has been proved to be
an effective way due to operational pressure, improved flux, and low energy requirement.

 Hybrid nano-membrane:
The hybrid membranes were developed to introduce additional functionalities such as adsorption,
photocatalysis, or antimicrobial activities(DK Baer.,2013). This can be achieved by simply
tuning the hydrophilicity of membranes, their porosity, mechanical stability and charge density.
Filteration and adsorption process can be coupled by using impregnated polysulfone with zeolite
nano-particle membrane for the removal of lead and nickel from the effluents.The sorption
capacity and hydraulic permeability of membrane could be improved by simple modification in
the membrane fabricating conditions and period of evaporation of the casting film.

 Beta  cyclodextrins:
The  use of  beta cyclodextrins  in textile industry  is of great significance  because it
enables the development  of fabrics that release chemical compounds  such as fragrances
and antimicrobial agents(PJ Rivero., 2015).  It is used to remove phenolphthalein and
fuchsin  acid by osmotic separation. The ability of beta cyclodextrins  to self- organize into
nanoparticles was tested using a nanoprecipitation  technique in various solvents.

Various technologies developed using nanoparticles to remove textile effluents:

Technology     Contaminant    
Efficiency  
Nano  filteration Fibre  reactive  dyes >80%
Photocatalysis  using nano fiber  Effluents  containing organic      75-95%
membrane solvents
Nanomembrane  with PGA(poly gamma Removal  of lead from  aqueous         99.8%
glutamic acid) solution(effluent)
Nanomembrane  coated with gamma- Removal  of COD and  BOD from     76-80%
alumina(nanocrystallites) textile  waste water
Nano structured  polymer based Oil  removal       99.75%
membrane
Electrospunnanofiber  membrane   Suspended  particles           95%
ZrO nanofilteration  membrane
2  Turbidity  and suspended  solids      
94.6%
(*References: Farhtun Nabi ., 2018)

Methods of eradicating the textile effluents using nanoparticles:

 By  using  chemicals:
Reactive  Blue 21 is  one of the dye  compound which is  harmful to human life,  a simple
method to remove  this pollutant from wastewater  effluent produced by textile industry 
is using Nano Zero-Valent Iron(NZVI) catalyst(SM Praveena.,2016).
Nickel nanoparticles  were synthesized which  is used to decolorize   dye effluent. Reactive Blue  21
was taken as reference dye,  and polyvinyl pyrrolidone(PVP) was used  as a stabilizer to
prevent agglomeration  of nanoparticles(JK Patra., 2014).
 By  the synthesis  of Ni-PVP nanoparticles requires:
I. Ethanol
II. NiCl .6H O
2 2

III. PVP
IV. Hydrazine hydrate
V. 1M  NaOH
VI. Heat upto 60˚C
VII. After  cooling,  add acetone(excess)

Vacuum dry Washed repeatedly with chloroform –

methanol solution

Vacuum filtered

PVP  stabilized  nickel nanoparticles  were synthesized and used  for decolorization of recalcitrant 
dye effluent. These nanoparticles gave decolourisation efficiency of 98.97% at optimized 
condition. Decolourisation also lead to the reduction in  COD of the effluent.
Characterization:  
  In the  absence of  dispersing agent,  Ni-nanoparticles are  agglomerated whose
particle  size is 29-243nm
 In  the presence  of dispersing agent(polyvinyl  pyrrolidone),  Ni-nanoparticles  are
not agglomerated  whose particle size is  20-44nm(J Zhang., 2017).

Outcomes and Benefits of Nanoparticles in Textile Effluent

Functionalities (water  repellence, UV resistance,  wrinkle resistance) of the textile  gets

improved

Enhancement of  functionalities of  textile by different  Nanomaterial type

Functio silver Zinc  Silica Titaniu alumina Nano  C – black

nalities  oxide m  clays
of oxide
textiles
Abras
ion 
resista
nce

Active 
resista
nce 
carriers

Antimi
crobial 
and
antista
tic
 Chemic
al 
resista
nce

Dirt  
repella
nt

Tensile 
strengt
h

UV –
absorp
tion

Water 
repelle
nt

Conclusion:

Industrialization and population are the main reasons for increase in amount of
wastewater. These are also the main areas which require the regular supply of clean water.
Several methods are employed to ensure a sustainable supply of water for the required
purpose. Nanotechnology is also being looked upon to provide economical, convenient and
eco-friendly means of wastewater reduction. Different size of nano particles such as nano sized
metals, nano filtration membranes have prove effective in detection, removal ad destruction of
contaminants.
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