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Chapter 1

INTRODUCTION AND OBJECTIVES

CONTENTS

1.1 THE PERSPECTIVE 2

1.2 BRIEF CHEMISTRY AND PROPERTIES OF DYES 6

1.2.1 Principles of Colour Chemistry

1.2.2 Considerations in the Design of Dyes

1.3 CRITERION FOR CLASSIFICATION OF DYES 11

1.3.1 Based on Chemical Structure

1.3.2 Based on Usage or Application

1.4 EQUIPMENT AND MANUFACTURE 16

1.5 TOXICOLOGICAL AND ENVIRONMENTAL


Chapter 1 Introduction And Objectives

CONSIDERATIONS 18

1.6 AIM AND SCOPE OF THE WORK 22

1.7 REFERENCES 22

1
1.1 The Perspective

Dyes may be defined as substances that, when applied to a substrate provides co-

lour by a process that alters, at least temporarily, any crystal structure of the coloured

substances. Such substances with considerable colouring capacity are widely employed

in the textile, pharmaceutical, food, cosmetics, plastics, photographic and paper indus-

tries. The dyes can adhere to compatible surfaces by solution, by forming covalent bond

or complexes with salts or metals, by physical adsorption or by mechanical retention.

Dyes generally have rather complicated structures which are made by reactions involv-

ing building blocks known as intermediates [1, 2]. Most of these are aromatic com-

pounds with substituent groups such as –NH2, -OH, -NO2 and –SO3H which alter the reac-

tivity of the cyclic compound and sometimes the color of the dye. Both inorganic and or-

ganic materials are needed to make dyes and intermediates, but the backbone of the

raw-material sequence is

Dyes add value to products far beyond their cost. Frequently the color of a product

is the reason for its sale. Some dyes have special uses, such as radiation detectors and

photosensitive product to his customer. Dyes sales in 1980 were estimated at $608 mil-
Chapter 1 Introduction And Objectives

lion. Every dye sale is estimated to influence $10 in product sales, so the effect is far

greater than the cost. Typical dye molecules appear complicated and confusing, but their

synthesis follows an orderly procedure, using about 1000 intermediates and compara-

tively few chemical conversions. A dye must be colored, but it must also be able to im-

part color to something else on a reasonably permanent basis before it can be consi-

2
dered as a dye. Most dyes contain considerable unsaturation, and some part of the dye is

usually in the form of aromatic rings with nitrogen unsaturation of several types com-

mon to many dyes, for example the quinoid structure which appears frequently. Many

correlations have been made and more attempted between chemical structure and color.

Color results from electronic transitions between molecular orbitals.

The term dyes and intermediates refers to those compounds which are prepared

from the original coal tar constituents by various chemical procedures and which, in

turn, can be converted into commercial dyes by relatively simple further transforma-

tions. A typical example is aniline, which is prepared from benzene in various ways, and

which can be converted into numerous dyes. The reactions used in the preparation of

intermediates are, for the most part, simple operations. Frequently, they proceed quanti-

tatively according to the rules of stoichiometry. In other cases, side reactions are en-

countered which complicate the reaction and greatly reduce the yield. It is one of the

important tasks of the dye chemist to study these undesirable side reactions sufficiently

to understand their nature and then, if possible, to select the reaction conditions which

will favor only the main reaction leading to the desired intermediate. This end is not al-

ways attained, because often the set of conditions which will eliminate the side reactions

is not known, but the chemist must always bear in mind the possibility of achieving
Chapter 1 Introduction And Objectives

these conditions by further study. The preparation of 1,8-aminonaphthol-3,6-disulfonic

acid (H-acid) illustrates this point. This compound has been known for nearly fifty years

and is still being studied extensively in many laboratories, yet to this day has not been

prepared in satisfactory yield. In many cases, so-called quantitative yields are obtained

but the product is not a pure compound. Thus, the reaction yields the calculated quantity

3
of product, but this is a mixture of isomeric or analogous compounds which must be se-

parated by some type of physical method. The isomeric nitrotoluenes (ortho, meta, and

para), for example, are always obtained in mixture, and special methods have had to be

evolved to separate the pure individuals economically. Sometimes a circuitous route can

be followed to arrive at an uncontaminated intermediate. In other cases, the reactions

are selected so as to prevent the formation of undesirable isomers as in the preparation

of "Tobias acid" (2-naphthylamine-l-sulfonic acid). This intermediate cannot be obtained

directly  from  β-naphthylamine, but can be prepared under the proper conditions from

β-naphthol. As mentioned, the basic operations of dye chemistry utilize simple chemical

reactions. An intermediate can frequently be prepared in several entirely different ways

and, in these cases, careful calculations must be made to determine which procedure is

most advantageous. The least expensive process is often not necessarily the best when

other factors are taken into account. For example, the question of apparatus may enter,

and calculations may show that it is uneconomical to purchase an expensive apparatus

for the process if a small quantity of the material is to be produced. Furthermore, con-

sideration must be given to the usability of the side products formed.

These often cannot be used at all (e.g. primuline), but may be valuable or even in-

dispensable in another process (e.g. chromium sulfate in the production of anthraqui-


Chapter 1 Introduction And Objectives

none). In evaluating a manufacturing procedure, the apparatus in which the operations

are carried out must always be considered. Unlike preparations done in the laboratory,

those in the plant cannot be carried out in glass equipment except in unusual cases. Fur-

thermore,  it  must  be  remembered  that  the  chemicals  often  attack  the  apparatus,  so  it’s  

amortizement is an important consideration [3].

4
The first synthetic dye, Mauveine, was discovered by Perkin in 1856. Since then

dyestuffs industry remains a vibrant, challenging industry requiring a continuous

stream of new products because of the quickly changing world in which we live. The ear-

ly dyes industry saw the discovery of the principal dye chromogens (the basic arrange-

ment of atoms responsible for the color of a dye). Indeed, apart from one or two notable

exceptions, all the dyes used today were discovered in the 1800s. The introduction of

the synthetic fibers nylon, polyester, and polyacrylonitrile during the period 1930-1950,

produced the next significant challenge. The discovery of reactive dyes in 1954 and their

commercial launch in 1956 heralded a major breakthrough in the dyeing of cottons; in-

tensive research into reactive dyes followed over the next two decades and, indeed, is

still continuing today. The oil crisis in the early 1970s, which resulted in a steep increase

in the prices of raw materials for dyes, created a drive for more cost-effective dyes, both

by improving the efficiency of the manufacturing processes and by replacing tinctorially

weak chromogens such as anthraquinones, with tinctorially strong chromogens such as

heterocyclic azo and benzodifuranone. These themes are still important and ongoing, as

are the current themes of product safety, quality, and protection of the environment.

There is also considerable activity in dyes for high-tech applications, especially in the

electronics and non impact printing industries [4, 5].


Chapter 1 Introduction And Objectives

The scale and growth of the dyes industry has been inextricably linked to that of

the textile industry. World textile production has grown steadily to an estimated 45 ×

106 t in 2000. The two most important textile fibers are cotton, the largest and polyester.

Consequently, dye manufacturers tend to concentrate their efforts on producing dyes for

these two fibers. The estimated world production of dyes in 2000 was 2.0 × 10 6 t [4].

5
Synthetic dyes are extensively used in many fields of up to-date technology, e.g., in vari-

ous branches of the textile industry, of the leather tanning industry in paper production,

in food technology, in agricultural research, in light-harvesting arrays, in photoelectro-

chemical cells, and in hair colorings [6-10]. Moreover, synthetic dyes have been em-

ployed for the control of the efficacy of sewage and wastewater treatment, for the de-

termination of specific surface area of activated sludge for ground water tracing, etc [11,

12]. Synthetic dyes exhibit considerable structural diversity. The chemical classes of

dyes employed more frequently on industrial scale are the azo, anthraquinone, sulfur,

indigoid, triphenylmethyl (trityl), and phthalocyanine derivatives. However, it has to be

emphasized that the overwhelming majority of synthetic dyes currently used in the in-

dustry are azo derivatives. It should be noted that azo-keto hydrazone equilibria can be

a vital factor in the easy breakdown of many of the azo dye system [13].

1.2 Brief Chemistry and Properties of Dyes

1.2.1 Principles of Colour Chemistry

Basis for colour Unlike most organic compounds, dyes possess colour due to four basic

characteristics, 1) absorption of light in the visible spectrum (400–700 nm), 2) have at

least one chromophore (colour-bearing group), 3) have a conjugated system, i.e. a struc-

ture with alternating double and single bonds, and 4) exhibit resonance of electrons,
Chapter 1 Introduction And Objectives

which is a stabilizing force in organic compounds [1]. When any one of these features is

lacking from the molecular structure the colour is lost. In addition to chromophores,

most dyes also contain groups known as auxochromes (colour helpers), examples of

which are carboxylic acids, sulfonic acid, amino, and hydroxyl groups. While these are

not responsible for colour, their presence can shift the colour of a colourant and they are

6
most often used to influence dye solubility. Table 1.1 shows the relationships between

wavelength of visible region and colour absorbed/observed.

Table 1.1 Wavelength of light absorption versus colour in organic dyes


Wavelength Absorbed (nm) Colour Absorbed Colour Observed
400–435 Violet Yellow-Green
435–480 Blue Yellow
480-490 Green-Blue Orange
490-500 Blue-Green Red
500-560 Green Purple
560-580 Yellow-Green Violet
580-595 Yellow Blue
595-605 Orange Green-Blue
605-700 Red Blue-Green

Other factors like chromophoric groups, conjugated systems and resonance, which con-

tribute to colour are illustrated in Figure 1.1. The structures in Figure 1.1b demon-

strate the importance of having an extended conjugated system. For a chromophore to

generate colour in organic compounds, it is important that it is a part of the conjugated

system. This is shown in Figure 1.2, where it can be seen that placement of an azo group

between methyl groups produces a colourless compound, while a yellow-orange colour

is obtained when the azo group is placed between aromatic rings.

Chapter 1 Introduction And Objectives

7
Figure 1.1 (a) Chromophoric groups present in organic dyes, (b) conjugated sys-
tems   in   vitamin   A   and   β-carotene and (c) resonance structures for malachite
green.

It is evident that doubling the length of the conjugated system in Vitamin A to give

β-carotene causes a significant bathochromic shift, i.e. to a darker colour.

Chapter 1 Introduction And Objectives

Figure 1.2 Chromophore within a conjugated system.


In addition to influencing solubility, auxochromes are essential ring substituents in

providing target colours. This is illustrated in Figure 1.3, where the following effects of

substituents are shown:

8
•   Adding groups of increasing electron-donating ability to the azobenzene structure

has a bathochromic effect (OH vs NH2).

•   Electron-donating (NH2) and electron-accepting (NO2) groups placed in conjuga-

tion provide a bathochromic effect. In this regard, nitro groups are especially bene-

ficial, contributing to their prevalence in disperse dye structures.

•   Increasing the number of electron-attracting groups conjugated with the electron-

donor has a bathochromic effect.

•   The electron-donating effects of an amino group are enhanced by adding alkyl

groups to the N-atom.

Figure 1.3 Substituent groups within an azo-dye system.


Dyes versus Pigments With regard to their solubility, organic colourants fall into two

classes, viz. dyes and pigments [2]. The key distinction is that dyes are soluble in water

and/or an organic solvent, while pigments are insoluble in both types of liquid media.
Chapter 1 Introduction And Objectives

Dyes are used to colour substrates to which they have affinity. Pigments can be used to

colour any polymeric substrate but by a mechanism quite different from that of dyes, in

that surface only colouration is involved unless the pigment is mixed with the polymer

before fibre or moulded article formation.

9
1.2.2 Considerations in the Design of Dyes

Dye-substrate Affinity Dyes containing one or more azo groups (i.e. azo dyes) com-

prise by far the largest family of organic dyes. Prominent types are 1) acid dyes for poly-

amide and protein substrates such as nylon, wool, and silk; 2) disperse dyes for hydro-

phobic substrates such as polyester and acetate, and 3) direct and reactive dyes for cel-

lulosic substrates such as cotton, rayon, linen, and paper. Generally, the synthesis of azo

dyes involves two steps. Step 1 is the conversion of an aromatic amine to a diazo com-

pound (i.e. Ar-NH2, Ar-N2+), a process known as diazotization, and step 2 is the reaction

of the diazo compound with a phenol, naphthol, aromatic amine, or a compound that has

an active methylene group, to produce the corresponding azo dye, a process known as

diazo coupling (e.g. Ar-N2+ +  Ar’-OH Ar-N=N-Ar’-OH). This process is suitable for forming

both azo dyes and pigments. Typical structures of colourants that fall into the two

groups are shown in Figure 1.4. Since the effectiveness of a dyeing or printing process

often hinges on the affinity between the dye and substrate, dyes are designed with a

specific substrate. In this regard, dyes must be designed that have a) greater affinity for

the substrate than the medium (usually water) from which it is applied and b) a high de-

gree of permanence under end-use conditions (e.g. stability to fading upon exposures to

water (wet fast) and/or sunlight (light fast)). The availability of colourants for a specific
Chapter 1 Introduction And Objectives

substrate type is the result of a deliberate molecular design process that takes the target

substrate and end-use application into consideration [15].

10
Figure 1.4 Some commercial azo dyes and pigments.

1.3 Criterion for Classification of Dyes

Dyes may be classified according to chemical structure or by their usage or appli-

cation method. The former approach is adopted by practicing dye chemists, who use

terms such as azo dyes, anthraquinone dyes, and phthalocyanine dyes. The latter ap-

proach is used predominantly by the dye user, the dye technologists, who considers

reactive dyes for cotton and disperse dyes for polyester. Very often, both terminologies

are used, for example, an azo disperse dye for polyester and a phthalocyanine reactive

dye for cotton [4].


Chapter 1 Introduction And Objectives

1.3.1 Chemical Structure

This system for the classification of dyes is by chemical structure, which has two advan-

tages, first, it readily identifies dyes as belonging to a group that has characteristic prop-

erties, for example, azo dyes (strong, good all-round properties, cost-effective) and anth-

11
raquinones dyes (weak, expensive) and second, there are a few (about a dozen) chemi-

cal groups for structural changes.

1.3.2 Usage or Application

Classification by usage or application is the principal system adopted by the Col-

our Index (CI) [16]. Because the most important textile fibers are cotton and polyester,

majority of the dye types are those which are used for dyeing these two fibers, including

polyester-cotton blends. Other textile fibers include nylon, polyacrylonitrile, and cellu-

lose acetate.

Reactive Dyes These dyes form a covalent bond with the fiber, usually cotton, although

they are used to a small extent on wool and nylon. This class of dyes, first introduced

commercially in 1956 by ICI, made it possible to achieve extremely high wash fastness

properties by relatively simple dyeing methods. A marked advantage of reactive dyes

over direct dyes is that their chemical structures are much simpler, their absorption

spectra show narrower absorption bands, and the dyeings are brighter. The principal

chemical classes of reactive dyes are azo (including metallized azo), triphendioxazine,

phthalocyanine, formazan, and anthraquinones.

Disperse Dyes These are substantially water-insoluble nonionic dyes for application to

hydrophobic fibers from aqueous dispersion. They are used predominantly on polyester
Chapter 1 Introduction And Objectives

and to a lesser extent on nylon, cellulose, cellulose acetate, and acrylic fibers.

Direct Dyes These water-soluble anionic dyes, when dyed from aqueous solution in the

presence of electrolytes, are substantive to, i.e., have high affinities for, cellulosic fibers.

Their principal use is the dyeing of cotton and regenerated cellulose, paper, leather, and,

to a lesser extent, nylon. Most of the dyes in this class are polyazo compounds, along

12
with some stilbenes, phthalocyanines, and oxazines. After treatments, frequently applied

to the dyed material to improve wash fastness properties, include chelation with salts of

metals (usually copper or chromium), and treatment with formaldehyde or a cationic

dye-complexing resin.

Vat Dyes These water-insoluble dyes are applied mainly to cellulosic fibers as soluble

leuco salts after reduction in an alkaline bath, usually with sodium hydrogensulfite. Fol-

lowing exhaustion onto the fiber, the leuco forms are reoxidized to the insoluble keto

forms and after treated, usually by soaping, to redevelop the crystal structure. The prin-

cipal chemical classes of vat dyes are anthraquinones and indigoid.

Sulfur Dyes These dyes are applied to cotton from an alkaline reducing bath with so-

dium sulfide as the reducing agent. Numerically this is a relatively small group of dyes.

The low cost and good wash fastness properties of the dyeing make this class important

from an economic standpoint.

Cationic (Basic) Dyes These water-soluble cationic dyes are applied to paper, polyacry-

lonitrile (e.g. Dralon), modified nylons, and modified polyesters. Their original use was

for silk, wool, and tannin-mordanted cotton when brightness of shade was more impor-

tant than fastness to light and washing. Basic dyes are water-soluble and yield colored

cations in solution. For this reason they are frequently referred to as cationic dyes. The
Chapter 1 Introduction And Objectives

principal chemical classes are diazahemicyanine, triarylmethane, cyanine, hemicyanine,

thiazine, oxazine, and acridine.

Acid Dyes These water-soluble anionic dyes are applied to nylon, wool, silk, and modi-

fied acrylics. They are also used to some extent for paper, leather, ink-jet printing, food,

and cosmetics.

13
Solvent Dyes These water-insoluble but solvent-soluble dyes are devoid of polar solubi-

lizing groups such as sulfonic acid, carboxylic acid, or quaternary ammonium. They are

used for coloring plastics, gasoline, oils, and waxes. The dyes are predominantly azo and

anthraquinone, but phthalocyanine and triarylmethane dyes are also used. The classifi-

cation of dyes according to their usage is summarized in Table 1.2.

Table 1.2 Classification of dyes based on usage/application

Class Principal Method of Chemical types


substrates application
Acid nylon, wool, silk, usually from neutral to azo (including
paper, inks, and acidic premetallized),
leather dyebaths anthraquinone,
triphenylmethane,
azine, xanthene, nitro
and nitroso

Azoic cotton, rayon, fiber impregnated with azo


components cellulose acetate coupling component
and and polyester and treated with a
compositions solution of stabilized
diazonium salt

Basic paper, applied from acidic cyanine, hemicyanine,


polyacrylonitrile, dyebaths diazahemicyanine,
modified nylon, diphenylmethane,
polyester and inks triarylmethane,
azo, azine, xanthene,
acridine, oxazine, and
anthraquinones

Direct cotton, rayon, applied from neutral or azo, phthalocyanine,


Chapter 1 Introduction And Objectives

paper, leather and slightly alkaline baths stilbene, and


nylon containing additional oxazine
electrolyte

Disperse polyester, fine aqueous disper- azo, anthraquinone,


polyamide, sions often applied by styryl, nitro,
acetate, acrylic and high temperature/ and benzodifuranone
plastics pressure or lower tem-
perature carrier meth-
ods; dye may be

14
padded on cloth and
baked on or
thermofixed

Fluorescent soaps and from solution, disper- stilbene, pyrazoles,


brighteners detergents, all sion or suspension in a coumarin, and
fibers, oils, paints, mass naphthalimides
and plastics

Food, drug, foods, drugs, and azo, anthraquinone,


and cosmetic cosmetics carotenoid
and triarylmethane

Mordant wool, leather, and applied in conjunction azo and anthraquinone


anodized with Cr salts
aluminium

Oxidation hair, fur, and aromatic amines and aniline black and
bases cotton phenols oxidized on the indeterminate
substrate structures

Reactive cotton, wool, silk, reactive site on dye re- azo, anthraquinone,
and nylon acts with functional phthalocyanine,
group on fiber to bind formazan, oxazine, and
dye covalently under basic
influence of heat and pH
(alkaline)
Solvent plastics, gasoline, dissolution in the azo, triphenylmethane,
varnishes, lacquers, substrate anthraquinone,
stains, inks, fats, and phthalocyanine
oils, and waxes

Sulfur cotton and rayon aromatic substrate indeterminate


vatted with sodium structures
sulfide and reoxidized
to insoluble sulfur-
Chapter 1 Introduction And Objectives

containing products on
fiber

Vat cotton, rayon, and water-insoluble dyes anthraquinone (includ-


wool solubilised by reducing ing polycyclic
with sodium quinones) and
hydrogensulfite, then indigoids
exhausted on fiber and
reoxidized

15
1.4 Equipment and Manufacture

There are usually several reaction steps or unit processes. The basic steps of dye

(and intermediate) manufacture are shown in Figure 1.5.

Materials Product Product drying,


Reaction grinding, and/or
Charging Isolation
finishing

Figure 1.5 Operation sequence in dye and intermediate manufacture.

The reactor itself, in which the unit processes to produce the intermediates and

dyes are carried out, is usually the focal point of the plant [4]. Operations subsequent to

reaction are often referred to as workup stages. These vary from product to product,

whereby intermediates (used without drying wherever practical) require less finishing

operations than colorants. The reactions for the production of intermediates and dyes

are carried out in bomb-shaped reaction vessels made from cast iron, stainless steel, or

steel lined with rubber, glass (enamel), brick, or carbon blocks. These vessels have ca-

pacities of 2-40 m3 (app. 500-10,000 gallons) and are equipped with mechanical agita-
Chapter 1 Introduction And Objectives

tors, thermometers, or temperature recorders, condensers, pH probes, etc., depending

on the nature of the operation. Jackets or coils are used for heating and cooling by circu-

lation of high-boiling fluids (e.g. hot oil or Dowtherm), steam, or hot water to raise the

temperature, and air, cold water, or chilled brine to lower it. Unjacketed vessels are of-

ten used for reactions in aqueous solutions in which heating is effected by direct intro-

16
duction of steam, and cooling by addition of ice or by heat exchangers. The reaction ves-

sels normally span two or more floors in a plant to facilitate ease of operation. Products

are transferred from one piece of equipment to another by gravity flow, pumping, or

blowing with air or inert gas. Solid products are separated from liquids in centrifuges, in

filter boxes, on continuous belt filters, and, perhaps most frequently, in various designs

of plate-and-frame or recessed-plate filter presses. The presses are dressed with cloths

of cotton, Dynel, polypropylene, etc. The plates and frames are made of wood, cast iron,

but more usually hard rubber, polyethylene, or polyester.

When possible, the intermediates are used for the subsequent manufacture of

other intermediates or dyes without drying because of saving in energy costs and han-

dling losses. This trend is also apparent with dyes. The use of membrane technology

with techniques such as reverse osmosis to provide pure, usually aqueous, solutions of

dyes has become much more prevalent. Dyes produced and sold as liquids are safer and

easier to handle and save energy costs. However, in some cases products, usually in the

form of pastes discharged from a filter, must be dried. Even with optimization of physi-

cal form, the water content of pastes varies from product to product in the range of 20-

80 %. Where drying is required, air or vacuum ovens (in which the product is spread on

trays), rotary dryers, spray dryers, or less frequently drum dryers (flakers) are used.
Chapter 1 Introduction And Objectives

Spray dryers have become increasingly important. They require little labour and accom-

plish rapid drying by blowing concentrated slurries (e.g. reaction masses) through a

small orifice into a large volume of hot air. Dyes, especially disperse dyes, that require

wet grinding as the penultimate step are now often dried this way. In this case their final

standardization, i.e., addition of desired amounts of auxiliary agents and solid diluents, is

17
performed in the same operation. The final stage in dye manufacture is grinding or mill-

ing. Dry grinding is usually carried out in impact mills. Dry grinding is an inevitable con-

sequence of oven drying, but more modern methods of drying, especially continuous

drying, allow the production of materials that do not require a final stage. The ball mill

has been superseded by sand or bead mills, while wet millings have become increasingly

important for pigments and disperse dyes.

1.5 Toxicological and Environmental Considerations

While dye–substrate affinity is critical, synthetic dyes cannot be commercialized

unless they pose little health risk under end-use conditions. Consequently, environ-

mental safety is an essential consideration in molecular design. In this regard, the raw

materials employed in the manufacture of synthetic dyes should not involve compounds

known to pose health risks. This would include a large group of aromatic amines [17]

that are either cancer-suspect agents or established mutagens in the standard Salmo-

nella mutagenicity assay [18]. It is clear, therefore, that dye design must take into con-

sideration the likely genotoxicity of the potential metabolites generated in mammalian

systems. In the case of azo dyes, the enzyme-mediated formation of genotoxic aromatic

amines as metabolites must be considered, since it is possible that the intact dye is safe

but not all of its metabolites. For instance, the use of Direct Red 28, an azo dye (Figure
Chapter 1 Introduction And Objectives

1.6) could lead to the formation of the bladder carcinogen benzidine if this dye were

taken up in the body.

Due to large-scale production and extensive application, synthetic dyes can cause

considerable environmental pollution and are serious health-risk factors. Although, the

growing impact of environmental protection on industrial development promotes the

18
development of ecofriendly technologies, reduced consumption of freshwater and lower

output of wastewater, the release of important amounts of synthetic dyes to the envi-

ronment causes public concern, legislation problems and is a serious challenge to envi-

ronmental scientists [19, 20]. Because of their commercial importance, the impact and

toxicity of dyes that are released in the environment have been extensively studied [21].

Figure 1.6 Reductive cleavage of Direct Red 28 using an azo-reductase enzyme.

As several thousand different synthetic dyes that are employed exhibit various

biological activities, it is understandable that our knowledge concerning their behaviour

in the environment and health hazards involved in their use is still incomplete. Tradi-

tional wastewater treatment technologies have proven to be markedly ineffective for


Chapter 1 Introduction And Objectives

handling wastewater of synthetic textile dyes because of the chemical stability of these

pollutants. A wide range of methods has been developed for the removal of synthetic

dyes from waters and wastewaters to decrease their impact on the environment. The

technologies involve adsorption on inorganic or organic matrices, decolorization by

photocatalysis, and/or by oxidation processes, microbiological or enzymatic decomposi-

19
tion, etc. [22]. The efficacy of the various methods of dye removal, such as chemical pre-

cipitation, chemical oxidation, and adsorption along with their effects on subsequent

biological treatment is also reported [23]. Chemical oxidation was very effective but the

efficiency strongly influenced by the type of oxidant.

Surveys in recent years have indicated that the textile industry is contributing in-

creasingly to the declining environment. Due to the use of strong chemicals like, strong

acids and alkalis, solvents, heavy metal catalysts, toxic amines and high temperatures,

these dyes are not fit to be released in the environment. However, as these chemicals

and dyes are used intrinsically in various processes in the textile industry, there is in-

creased land and water degradation. This causes a serious threat to the surroundings.

This also constantly forces the industry to increase its efforts on improving processes

and minimizing the harmful effects to the environment [24-26].

The biggest contributors to the pollution from textile industry are the dyeing and

finishing processes. The main problem or difficulty encountered with treating these

dyestuffs is that these are highly complex structures and hence not easily bio-

degradable. So it becomes difficult to separate them from the waste water released into

the water bodies [27, 28]. Approximately 2 % of dyes produced annually and discharged

into effluent are from manufacturing operations while 10 % of dyes are discharged in
Chapter 1 Introduction And Objectives

effluents from textile and associated industries [29]. Various efforts have been made in

the direction of synthesizing new types of dyes molecules and waste water treatment so

as to reduce the level of water pollution resulted in due to this industry out of which few

have been successful viz. coagulation/flocculation, reverse osmosis techniques, and acti-

20
vated carbon absorption [30]. However, these methods result in transferring the conta-

minants from one phase to the other while leaving the problem as it is [31].

Degradation of dyes occurs by anaerobic microorganisms by reducing their nitro-

gen bonds, which results in forming of toxic, carcinogenic compounds due to the afore-

mentioned biological degradation [32-34], though one can regain the color by making

contact of oxygen with the anaerobic degradation products [35]. Color removal is re-

stricted in big amounts by these problems using bacteria. Photocatalysis is one of the

newer methods. It is an Advanced Oxidation Process, used to mineralize dye compounds

[36, 37]. TiO2 is being increasingly used and can be used in the development of a useful

process for reducing water pollution caused by dyeing compounds due to their efficien-

cy in the mineralization and the mild conditions required. In addition, it can oxidize

most of the organic contaminants to CO2 and H2O [38, 39]. It is common and well known

that in order to decrease water pollution, the fixation levels of reactive dyes need to be

increased. The main reactive system for cellulose has been firmly established as the

chlorotrazinyl and vinylsulphone groups. Due of this, reactive dyes with more than one

reactive group in the dye molecule have been the subject of continuous investigations.

Classification of reactive groups is done on the basis of the number of reactive groups

contained in the dye molecule, as mono-, bi- and poly-functional reactive systems [40].
Chapter 1 Introduction And Objectives

Such dye properties can be achieved by appropriately modifying the molecular structure

of the dye.

21
1.6 Aim and Scope of the Work

The main objectives of the present research are,

1. To synthesize new modified reactive dyes with 3-sulphonyl 4-amino phenyl beta

hydroxy ethyl sulphone sulphate ester (sulfo para vinyl sulfone) reactive group.

2. Scale-up of laboratory synthesis of dyes to the manufacturing level in an industry.

3. Standardization of dyeing variables of synthesized reactive dyes for cotton fiber.

4. To evaluate the exhaustion and fixation values of newly synthesized dyes and to

study their fastness to commercial detergents on cotton fabric.

5. Explore the efficiency of TiO2 for development of process efficient and as cost effi-

cient material to promote sufficient waste water treatment with the synthesized

dyes.

6. Decolorization of synthesized dyes under various environmental conditions.

1.7

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25