INTRODUCTION:

A note on world population, results in industrialization and urbanization, this in

turn results in increased consumerism. Industrialization is a process of social and
economic change whereby a human society is transformed from a pre-industrial to an
industrial state (www.industrialization.com).

Among various basic necessities, clothing is very essential. Population explosion

urges the expansion of industrial sectors. Of various industries, textile industries play an
important role, not only in meeting the demand, also in the upliftment of Indian economy.
It is very clear that these industries play an important positive role in Indian economical
reformation, though on the other hand they contribute to the aspect of pollution.(Geetha
et al., 2004).

TEXTILE/ DYEING INDUSTRY:

The dyeing industry is an important sector of the chemical industry. Dyes are
widely used in textiles, paper, leather, fur, drugs, cosmetics, wax, grease, and plastics
industry.

The Indian textile industry is one of the largest in the world with
a massive raw material and textiles manufacturing base. It contributes
about 14% to the national industrial output and about 25% to the total
national export earnings. Our economy is largely dependent on the
textile manufacturing and trade in addition to other major industries.
About 27% of the foreign exchange earnings are because of export of textiles and
clothing alone. The textiles and clothing sector contributes about 14% to the industrial
production and 3% to the gross domestic product of the country. Around 8% of the total
excise revenue collection is contributed by the textile industry.

Annually, more than one million tons of different synthetic dyes and pigments are
produced. In India about 82% of textile industries are using cotton fiber and remaining
18% are synthetic fibers .The total capacity employed in this industry is over 13000
million rupees and it provides employment to about 3 million people .

The textile industry in India is a key sector in terms of

employment as it is the second largest employment provider after
agriculture. So much so, the textile industry accounts for as large as 21% of the total
employment generated in the economy. Around 35 million people are directly employed
in the textile manufacturing activities. Indirect employment including the manpower
engaged in agricultural based raw-material production like cotton and related trade and
handling could be stated to be around another 60
million.(http://texmin.nic.in/tnpl_chap1.pdf)

In recent years, the textile industry has undergone

modernization. In addition to the conventional fibres (cotton, synthetic,
wool), variety of fibres and blends have been introduced. The latest
developments include new machineries that process more fabric per
unit time and conserve water, varied types of dyes have also been
introduced. Even the character of an effluent released from the
processing of the same type of fabric will vary from mill to mill.
(Manivasakam, 1995).

India's dye industry produces much type of dyes and pigments. Production of
dyestuff and pigments in India is close to 80,000 tonnes. %. As the textile industries need
to satisfy the ever-growing demands in terms of quality, variety, fastness and other
technical requirements their growth is higher along with an increase in the dye production
too. However, a recent study conducted under the National Biodiversity strategy and
Action Plan (BSAP) has revealed that chemical colors have all but wiped out India’s
wonderful vegetable dyes.

Out of various activities in textile industry, chemical processing

contributes about 70% of pollution. Due to the nature of various
chemical processing of textiles, large volumes of waste water with
numerous pollutants are generated. Approximately, 106 kg/year of dyes
are discharged into waste streams by the textile industry world-wide.

Nearly 10000 dyes and pigments are used in dyeing and printing industries
.Globally about 7X105 tones of dyes are produced annually of which 10-15% flow out in
the effluent during dyeing process (Meyer,1981, Zollinger ,1987).

Synthetic dyes like triphenylmethane and azo dyes are extensively used in textile
industries for dyeing of nylon , polyacrylon nitrile modified nylon , wool , silk and
cotton (Gregory , 1993)

DYES:

Substance called dye, if it satisfies certain conditions, such as.,

1. It must have a suitable color.

2. It must be capable of being fixed to the fabric directly or with the
help of certain reagents called mordant.
3. When fixed it must not be fugitive that is the color must be fast o
light, resistant to soap, water and to a certain extent to dilute
acids and alkalis.

Also,

In short, dyes are colored, ionizing, aromatic organic compounds. From definition,
dyes are aromatic compounds their structure includes aryl rings, which have delocalized
electron systems. These are responsible for the absorption of electromagnetic radiation of
varying wavelengths, depending on the energy of the electron clouds.
 Dye is a combination of chromophore and auxochrome.

CHROMOPHORE:

Colored compound contain certain unsaturated group is called chromophore.

Chromophores are atomic configurations that contain delocalised electrons. By
incorporating the delocalised electrons in these configurations into the delocalised
electrons in the aryl rings of aromatic compounds, the energy contained in the electron
cloud can be modified which leads to change in the wavelength to be absorbed in the
visible range, then the compound will be colored.

It was first explained by O.N.WITT in 1876.

Below are the usual chromophores seen in histological dyes:–

–NO2 (nitro) –N=N–(azo) >C=O(keto) >C=S(thioketo) >N=O(nitroso)

Ortho- and para- quinoid ring chromophores

AUXOCHROME:

Compound with chromophore is called as chromogen. When chromogen contains

other groups is called as auxochrome. Also auxochromes are groups which attach to non
ionizing compounds yet retain their ability to ionize.

The word auxochrome is derived from two roots. The prefix auxo is from auxein,
and means increased. The second part, chrome means colour, so the basic meaning of the
word auxochrome is colour increaser.

The auxochrome may be either acidic or basic like –OH or NH 2, other

auxochrome include –SO3H, -NR2, -NHR.

SOURCES OF DYES:

1. Natural dyes 2.Synthetic dyes

NATURAL DYES:

It was practiced during the Bronze Age in Europe. Natural matter was used to
stain hides, decorate shells and feathers, and in cave paintings. Scientists have been able
to date the black, white, yellow and reddish pigments made from ochre used by primitive
man in cave paintings.
 Natural dyes are a class of colorants extracted from vegetative matter and animal
residues. These are considered as mordant dyes as they require the inclusion of one or
more metallic salts of aluminium, iron, chromium, copper and others for ensuring
reasonable fastness of the colour to sunlight and washing. These metallic salts combine
with the dye stuff to produce dye aggregates which cannot be removed from the cloth
easily.

Based on affinity, natural dyes are classified as,

 Substantive natural dyes: Applied directly to fabric. Eg., Indigo, Turmeric

 Adjective natural dyes: Applied directly to fabric in presence of mordant/
metallic salts. Eg., Madder, Cochineal.

MORDANT:

Dyes do not interact directly with the materials they are intended to colour.
Natural dyes are substantive and require a mordant to fix to the fabric, and prevent the
colour from either fading with exposure to light or washing out. These compounds bind
the natural dyes to the fabrics. A mordant is an element which aids the chemical reaction
that takes place between the dye and the fibre, so that the dye is absorbed.

Based on chemical structure they are classified into the following groups,

 Indigo dyes
 Anthroquinone dyes
 Alpha-hydroxy naphthoquinones
 Flavones
 Dihydropyrans
 Anthocyananidins
 Carotenoids

Natural dyes are obtained from,

Plants, animals and minerals.

Natural dyes obtained from plants:

Many natural dyestuff and stains were obtained mainly from plants and dominated
as sources of natural dyes, producing different colors like red, yellow, blue, black, brown
and a combination of these. Almost all parts of the plants like root, bark, leaf, fruit, wood,
seed, flower, etc. produce dyes.

Eg., Roots of madder, leaves of wood, leaflets and branches of indigo.

Natural dyes obtained from animals:

Cochineal is a brilliant red dye produced from insects living on cactus plants. The
properties of the cochineal bug were discovered by pre-Columbian Indians, who dried the
female insects under the sun, and then ground the dried bodies to produce a rich red
powder. When mixed with water, the powder produced a deep, vibrant red colour.
Cochineal is still harvested today on the Canary Islands. In fact, most cherries today have
a bright red appearance through the artificial colour ‘carmine’, which is obtained
from the cochineal insect.

Natural dyes obtained from minerals:

Ocher is a dye obtained from an impure earthy ore of iron or ferruginous clay,
usually red (hematite) or yellow (limonite). In addition to being the principal ore of iron,
hematite is a constituent of a number of abrasives and pigments.
(http://www.ias.ac.in/currsci/apr102007/916.pdf)

SYNTHETIC DYES:

William Henry Perkin, the inventor of the first synthetic dye, started production of
aniline purple better known as mauveine near London at the end of 1857 and remained
the only producer for at least a few months.

Synthetic dyes were invented in the 1860s. Synthetic dyes quickly replaced the
traditional natural dyes. They cost less, they offered a vast range of new colors, and they
imparted better properties upon the dyed materials.

CLASSIFICATION OF SYNTHETIC DYES:

Based on the structure:

 Anthraquinone
 Alpha napthaquinone
 Flavones
 Anthracyanins
 Indigoids
 Dihydropyrans
 Carotenoids
 Polyhydric phenol

Based on their application:

 Acid dyes
 Basic dyes
  Direct dyes
 Azoic dyes
 Disperse dyes
 Fiber reactive dyes
 Vat dyes
 Mordant dyes
 Solvent dyes
 Sulfur dyes

REACTIVE DYES:

Reactive dye is a class of highly soluble colored organic substances primarily

utilized for tinting textiles, which attach themselves to their substrates by a chemical
reaction that forms a covalent bond between the molecule of dye and that of the fibre in a
weak alkaline dye bath.

Of all, Procions are the first successful reactive dyes for dyeing and printing of
cellulose fibres.

HISTORY:

Reactive dyes first appeared commercially in 1956, after their invention in 1954
by Rattee and Stephens at the Imperial Chemical Industries Dyestuffs Division site
in Blackley, Manchester, United Kingdom.

The general structure of a fibre-reactive dye is shown below:

CHEMISTRY OF REACTIVE DYES:

To make a permanent bond between the dye and the cotton dye and washing soda
were added; also sodium carbonate was added before or after the addition of dyes. After a
while chlorines and hydrogen will come out of dye and cellulose molecules respectively.
Then the dyes attach to the cellulose and a permanent bond is formed.

CLASSIFICATION:

Reactive dyes are classified based on chlorine atom attached to the triazine ring.

COLD BRAND REACTIVE DYES:

When two chlorine atoms are present in the dye molecule, one of the chlorine
atoms is so reactive that it can be dyed with cellulose even at room temperature (20-
300C), in the presence of alkali.
Eg., Dichlorotriazane dyes

HOT BRAND REACTIVE DYES:

Under alkaline condition, when only one chlorine is present in the dyestuff
molecule, the reactivity of the dye decrease considerably and dyeing has to be carried out
at a higher temperature (65-80o C).
Eg., Cibacron brilliant red – B

Procion H and Cibacron ranges of dye were introduced in 1957 by ICI and CIBA.

IMPACTS:

Liquid effluents constitute by far the largest proportion of total waste in the textile
industry. To protect the environment from the adverse impact of effluents they have to be
treated to the limits stipulated by the Pollution Control Board and River authorities.
Textile effluents are generally intensely colored; contain both suspended and soluble
organic and inorganic impurities and passes high BOD and COD. They are of highly
polluting nature and disposal of them without any treatment affects the environment,
especially the watercourses in several ways.

EFFECTS ON WATER COURSES:

1. COLOR:
The effluents contain dyes and higher concentrations that impart color to the
receiving streams and they persist for longer distances. Photosynthesis of phytoplanktons
is affected by these colors.

2. SUSPENDED IMPURITIES:
The colloidal and suspended impurities produce turbidity in the receiving waters.
The turbidity together with color causes an unsightly appearance.

3. pH VALUE:
The extreme alkalinity makes the receiving waters alkaline, it is deleterious to
aquatic life, and the water becomes unsuitable for other purposes too.
4. OILS AND GREASES:
Various oils, especially mineral oils in the effluents interfere with the oxygenation
of streams as they forms blanket on the surface and prevents the entry of oxygen at
air/water interface.

5. DISSOLVED MINERALS:
The dissolved inorganic matter, (mostly sodium salts) increase the salinity of
water and consequently it becomes unfit for irrigation.

6. TOXIC SUBSTANCES:
Chromium, Sulfide, chlorine and aniline dyes present in the textile wastes are
toxic to fish and microbial organisms which carryout purification. Thus, the self-
purification of the water body is affected.

7. DEPLETION OF OXYGEN:
Substances present in the textile effluents (such as starch, dextrin, sulfide, nitrite
etc.,) exert an oxygen demand. The stream will then be devoid of oxygen and the aquatic
lives are affected adversely

EFFECTS ON LAND:

1. The excess content of sodium and boron of the textile wastes are deleterious to crops.
2. The high sodium alkalinity combined with the salinity impairs the growth of plants.
3. Texture of the soil is affected by suspended impurities and sodium, and penetration of
roots is prevented.

PROCESS INVOLVED IN DYEING INDUSTRY:

After the raw natural or manufactured fibers are shipped from the farm or the chemical
plant, they pass through four main stages of processing :

• Yarn production

• Fabric production

• Wet process

• Garment Manufacturing

YARN FABRICATION
Yarn fabrication is the process, which converts raw fiber into yarn or thread.

FABRIC PRODUCTION
Fabric production, the second step, involves weaving, knitting, tufting and non-woven.
FABRIC PROCESSING (WET PROCESSING)
The main operations carried out in this step include pre-treatment, dyeing, printing and
finishing.

Pre-treatment
The pre-treatment process is carried out to prepare the textile material for
subsequent processing, which includes dyeing, printing and finishing. The main
operations include:

Desizing
In this process, the sizing ingredients were removed from the grey fabric by
dissolving them with acid or enzymes etc., then removes size from the fabric, so that
chemical penetration of the fabric in later stages is not inhibited.

Scouring
The scouring process is carried out to remove impurities such as wax, fatty acids,
oils, etc, present in the fabric. Scouring is carried out in alkaline conditions (with sodium
hydroxide) under high pressure and temperature (above 100oC).

Bleaching
Bleaching is used to whiten fabrics and yarns. Different chemicals such as
hypochlorites, hydrogen peroxides, etc, are used as bleaching agents. Once bleaching is
complete, the bleaching agent must be completely removed, either by thorough washing
or through the use of enzymes.

Mercerizing
Mercerizing increases the tensile strength, luster and dye uptake of the cotton
fabric or yarn. In this process, the cotton yarn or fabric is treated with cold sodium
hydroxide solution. This causes swelling of the fiber, which results in an increase in the
dye intake. Excess sodium hydroxide is normally recovered for reuse in either the
scouring or other mercerization stages.

Dyeing

Dyeing is employed to give an all-over shade to the fabric. It basically involves

diffusion of dye molecules into the textile fabric, which imparts the required color. In the
dyeing process these dye particles quickly come into contact with the surface of each
fiber, form a thin layer and diffuse into it . There are essentially two techniques available
for dyeing the textile material. These are:

Batch technique:
 The liquor and the textile are placed together in a vessel and the required amount
of dye is added.

Continuous technique:
The dye is dissolved or dispersed in the liquor. A definite quantity of dye liquor is
locally applied to the textile.

Printing
Printing is a process by which colored patterns are produced on the fabric. The
most commonly used printing techniques are:
Pigment printing, Wet printing, Discharge printing.

Finishing
This stage includes the final operations necessary for making the textile
presentable and attractive. It imparts the final aesthetic, chemical and mechanical
properties to the fabric as per the end use requirements.

Depending upon the type of fabric to be processed and the final product, any or all of the
above processing operations can be carried out. Each of these operations involves
consumption of huge quantities of water and chemicals.

AMOUNT OF EFFLUENT GENERATED FROM VARIOUS TEXTILE PROCESSING

UNITS:

PROCESS AMOUNT OF EFFLUENT GENERATED/1000KG

OF PRODUCT PRODUCED

Sizing 500 – 8200 litres

Desizing 2500 – 21000 litres

Scouring 19000 - 43000 litres

Bleaching 2500 – 125000 litres

Mercerizing 17000 – 34000 litres

Dyeing 166500 litres

 Printing and Finishing Much less

SCHEMATIC DIAGRAM FOR THE TREATMENT OF DYEING: