POLLUTION CONTROL IN DYE

INDUSTRY
 Introduction
 A dye can generally be described as a colored substance
that has an affinity to the substrate to which it is being
applied. The dye is generally applied in an aqueous solution,
and may require a mordant to improve the fastness of the dye on
the fiber
 Both dyes and pigments appear to be colored because they
absorb some wavelengths of light preferentially. In contrast
with a dye, a pigment generally is insoluble, and has no
affinity for the substrate.

Electronic excitation energies

 σ → σ*
 π → π*
 n → σ*
 n → π*
 aromatic π → aromatic π*

Chromophore: it is a functional groups which are unsaturated

and they cause a compound to become coloured.
Examples of chromophores are –N=N-, -C=C-, -C=N- and
-C=O.
1. Transitions involving σ, π, and n electrons
2. Transitions involving charge-transfer electrons
3. Transitions involving d and f electrons
 Auxochrome
 Auxochromes are groups that does not impart color to
the compound but increase the color of the compound.
Functional groups such as hydroxyl (–OH), amino ( -NH2),
nitro (-NO2), alkyl (-R), —OH, —OR, —NH2, —NHR, —
NR2, —SH are common examples for auxochrome. The
effect of the auxochrome is due to its ability to extend
the conjugation of a chromophore by the sharing of
non-bonding electrons.

 Bathochromic Effect
 Hypsochromic shift
 Hyperchromic Effect
 Hypochromic Effect
 Pictorial representation of
bathochromic shift and hypsochromic
shift in the absoption spectra

Typical data on some chromophre

 CLASSIFICATION OF DYES
 Acid Dyes
These are generally applied to textile fibers from
dye baths containing acid. Most have one or two
sodium sulfonate (–SO3Na) groups which are
water soluble and capable of bonding with fibers
having cationic sites. They give a wide range of
bright colors on textiles, especially when
monoazo and anthraquinone structures are used.

Basic dyes
Basic dyes were developed to dye negatively
charged acrylic fibers, forming ionic bonds.
They owe their name to the presence of aromatic
amino (basic) groups, and in this case a
cationic amino group is present. Generally,
they have excellent brightness and color
strength, their lightfastness is often Low.
 Direct dyes
Direct Dyes or substantive
dyeing is normally carried out in a
neutral or slightly alkaline
dyebath, at or near boiling point,
with the addition of either
sodium chloride (NaCl) or
sodium sulfate (Na2SO4).
Direct dyes are used on cotton,
paper, leather, wool, silk and
nylon. They are also used as pH
indicators and as biological stains.
 Direct dyes are anionic
colorants that have affinity for
cellulosic fibers. They were the
first dyes with the ability to dye
cotton in the absence of a
mordanting agent, giving rise
to the term direct-cotton dyes.
 Sulfur Dyes
Sulfur dyes are water-
insoluble dyes that are
applied to cotton. These are
mainly give dull shades. While
yellow, red, brown, olive,
and blue colors can be
produced, sulfur dyes are
most important for their
ability to deliver washfast
black shades on cotton
Examples of (a) sulfur yellow and
(b) red dye structures

Azo Dyes: It is a technique in which an insoluble azoic dye is produced

directly onto or within the fibre. This is achieved by treating a fibre with
both diazoic and coupling components. With suitable adjustment of dyebath
conditions the two components react to produce the required insoluble azo
dyes.
This technique of dyeing is unique, in that the final color is controlled by the
Vat Dyes:
 Water insoluble and fast dyes
applied along with strong reducing
agents (sodium hydro sulfite) and
alkali to make the dye soluble.
 The cloth is then exposed to air for
oxidation.
 The excess alkali remaining on the
cloth is neutralized by scouring.
 Vat dyes have mainly anthraquinone
(82%) or indigoid/thioindigoid (9%)
structures, with the former having
better fastness properties Representative Anthraquinone vat dye
 Vat dyes are easier to reoxidize than structures (a) Vat Red 13, (b) Vat
sulfur dyes and the oxygen in air is Black 27, (c) Vat Orange 2, (d) Vat Blue 4,
often the agent used. As would be and (e) Vat Green 1.
anticipated, most vat dyes display
high wash fastness
 DYESTUFF INDUSTRY TREATMENT

The presence of residual color, high levels of electrolytes, toxic substances

(e.g., metals and unreacted raw materials) in dye application processes
produce wastewaters that poses unacceptable environmental risks.

In the case of textile dyeing operations, the concerns raised can arise from
incomplete dye bath exhaustion and the presence of dyeing auxiliaries and
metal ions that are toxic to aquatic life.
 Sources of effluent
 Dyeing and printing
 industries
 Textile industries
 Paper and ink manufacturing industries
 Cosmetics
 Pharmaceuticals
 Food
 Properties of effluent
 Impart colour to water bodies even if present in small quantity
 Reduces light penetration and photosynthesis
 Carcinogenic or mutagenic
 Azo dyes are more toxic as they affect microbes thereby affecting
biological degradation treatment.
 Dyes increases BOD of effluent thereby affecting aquatic life
 Toxic to fish & microbial organisms
 The discharge of heavy metals into aquatic ecosystemsIncrease in
alkalinity of water
 The turbidity and colour along with oil and scum create an unsighty
appearance.
 The mineral materials, mostlysodium salts increase salinity of the
water.
 Volume of effluent

 The volume of effluent generated in dyeing is

comparatively more.
 It contains dyes, mordants, acids (acetic acid), alkalis,
nitrites, chromium salts, sodium chloride and soaps.
 These effluents are usually hot, highly coloured with a
high pH and sulfide content
 Care must be taken while neutralising these liquors as acid
may liberate hydrogen sulfide gas.
 Removal of Sulfides by treatment with chlorine or
hypochlorites
 Spent vat dyes are strongly alkaline and have fairly high
permanganate value
 Effluent Treatment Methods
Physical Methods
Adsorption
 Activated carbon adsorption has been widely studied as a
waste treatment method for the removal of different classes of
dyes from wastewater.
 Factors such as the choice of activated carbon,
temperature, pH, contact time, and dosage must be taken into
consideration for optimum removal of dyes from wastewater
 The most commonly used method of dye removal by
adsorption. It can be Effective for adsorbing cationic, mordant
and acid dyes and reactive dyes
 Performance depends on the type of carbon used and the
characteristics of the wastewater.
 Equalization
Regulation of flow rate, also maintains pH levels of the system.

Neutralization
Adsorptive Bubble Separation

Surface-active material, which

may be ionic, molecular,
colloidal, or macroparticulate in
nature, is selectively adsorbed
at the surface of bubbles rising
through the liquid.
98—99.8% of Direct Blue1 was
removed from wastewater
 Chemical methods

 Fenton’s reagent (Fe2/H2O2) has been used commercially to

oxidize and decolorize effluents containing a number of azo,
anthraquinone, and reactive dyes.
 Dyes removed in these studies include reactive azo and
anthraquinone dyes.

Titanium Dioxide (TiO2)

 The cationic dye Rhodamine B, Basic Violet 10 and the
anthraquinone mordant dye Alizarine Red (Mordant Red 3)
can be decomposed by Ti02 in the presence of visible light.
Degradation occurs via the interaction of dye with hydroxyl
radicals (OH.). Two of the final degradation products are
phthalic acid and carbon dioxide.
 Borohydride Reduction
 Sodium borohydride is one of the strongest water soluble reducing
agent commercially available

 SO2 is produced when borohydride is used in combination with

bisulfite catalysis in the pH rang e of 5 – 8 which readily
reduces azo dyes

 The utility of this process involving a variety of azo dyes,

giving percent colour reduction of 83-99% for acid, direct, and
reactive dyes and 74-99.9% for metalized direct and
phthalocyanine dyes

 This method was extended to industrial wastewater containing either

a mixture of azo disperse dyes or azo reactive black dyes.
 These solutions were treated with a mixture of 400—500 mg/L
Na2S2O5, 12—25 mg/L NaBH4, and 0—200 mg cationic flocculant,
Structures of dyes removed using biological treatments: Acid Blue 113
(13), Acid Yellow 17 (14), Direct Red 16 (15), Disperse Blue 73 (16),
and Vat Golden Yellow
 Bioaugmentation and Bioremediation

These methods are

currently used by the
textile and dyestuff
industries to decolorize
waste water using enzymes.
In this regard, enzymes
such as laccases, lignin
peroxidases, and manganese
peroxidases have proved
effective in cleaving
aromatic rings

Structures of dyes used in borohydride reduction studies: (1) direct Red 254,
(2) direct yellow 4, (3) acid red 1, (4) acid red 361, (5) reactive red 24, (6) reactive
red 120
 Metal Complexed Dyes

 One of the most serious environmental

problems in the dye, textile, and leather
industries is associated with the
manufacture and use of metallized azo
dyes that are complexed with chromium or
cobalt to obtain desirable fastness properties
 various chemical, physical, and biological
methods, such treatments can be
expensive and may result in sludges that
must be disposed by incineration or land
filling
 In view of an emphasis on pollution
prevention instead of waste treatment, the
merits of substituting iron (Fe) for
chromium (Cr) and cobalt (Co) in a group of
commercially important acid dyes.
 Fe-complexed dyes as environmentally
friendly alternatives to widely used Cr and
Co complexed acid dyes
 Electrodialysis

 The ionic components (heavy metals) are separated through

the use of semi-permeable ion­selective membranes.
 Application of an electrical potential between the two
electrodes causes a migration of cations and anions
towards respective electrodes
 Because of the alternate spacing of cation and anion
permeable membranes, cells of concentrated and dilute salts
are formed
 Membrane Bioreactor in Textile Waste Water Treatment
 Utilization of membrane filtration results in the retention of active micro-
organisms, extra cellular enzymes generated by these micro-organisms
for degradation of the organics present in the effluent
 Some micro-organisms, especially nitrifiers, are slowly growing one, their
loss shall reduce the efficiency of the treatment system and nutrient
removal
 In the MBR, these organisms are retained and a better treatment is
achieved
 In addition retention of active enzymes secreted by mico organisms taking
part in the metabolization of organics present in the textile waste water is an
important aspect of MBR technology
 Maintenance of higher concentration of these enzymes shall result in
rapid and better degradation of complex organic molecules present in the
textile waste water.
 The overall efficiency of BOD (Biological Oxygen Demand) and COD
(Chemical Oxygen Demand) removal is improved
 MBR is normally designed to incorporate two zones viz., i) anoxic; ii)
aerobic

 Some bacteria can use oxygen as an electron acceptor when it is available,

and in the absence of oxygen the same bacteria can switch the
respiration mode to utilize nitrate/nitrite as electron acceptors (facultative
bacteria) and these can be used in both in anoxic as well as in aerobic
conditions
 As MBR configuration involves anoxic, aerobic, and membrane
compartments with re-circulation from the membrane zone to the anoxic
zone, the anoxic zone shall have very low levels of dissolved oxygen
brought back by the recirculating effluent.
 The bacteria growing under anoxic condition has the capability to
break down recalcitrant macromolecules, which is then digested by the
aerobic bacterial population persisting in the aerobic zone.
 In this way, a significant portion of the dye stuff and other organics could
be broken down and oxidized. Thus, anoxic biological degradation is an
important step if we consider MBR treatment for textile waste water

Recirculation pattern inside MBR
compartments
This stabilized output water
quality is due to the
prevalence of a steady-state
condition inside the MBR
compartments due to the
maintenance of high microbial
activity
If X is the inflow, and therefore
outflow, anaerobic to aerobic and,
aerobic to membrane flow is 4X,
with a recirculation from membrane
compartment to anaerobic being 3X
When ever the feed quality
changes, its characteristics are
dampened by this re-circulation as
the feed waste water gets diluted by
the re-circulating fluid, and any
oscillations in effluent parameters are
dampened
The dampening effect shall be linear
for all parameters having linear
relationship with concentration viz.,
BOD, COD, TDS (Total Dissolved
Solids
 Advantages of MBR

 Membrane Bioreactors have proven to be quite effective in removing

both organic and inorganic contaminants as well as biological entities
from waste water.
 The removal of organic, inorganic, and microbiological organisms along
with suspended material present an excellent output from these systems
whereby the biofouling and chemical scaling of the reverse osmosis
system could be drastically minimized.
 It also minimizes use of cleaning chemicals in the secondary
treatment.
 High molecular weight organic compounds, which are not readily
biodegradable in conventional systems, are retained in MBR. Thus, their
residence time is prolonged and the possibility of biodegradation is
improved.
 REFERENCES

 1. www.wikipedia.org
 2. Y. R. Sharma, Elements of organic spectroscopy, S. Chand
& Company LTD, New Delhi, India.
 3. Kirk – Othmer, Encyclopedia of chemical technology, 5th
 Edition, 9th Volume, Wiley Interscience, John Wiley & Sons,
Inc., Publication
 4. S.Eshwaramoorthi, K. Dhanapal and D.S.Chauhan,
Environment With People's Involvement & Co-ordination in
India, Coimbatore, India, www.ecpconsulting.in
 5. http://www.scribd.com/doc/12949482/Dyestuff-Industry-
Treatment, 2003
Thank you