Dyestuff Industry

Treatment
Dyestuff Industry
 Three sub-segments, namely
dyes, pigment and
intermediates.

 The dye intermediates are

petroleum downstream products

 These are essential inputs in

major industries like textiles,
plastics, paints, paper and
printing inks.
Types of Dyes
 Direct dyes:
 Small dyeing houses
 Easy to apply
 No auxillary chemicals

 Basic dyes:
 Bright colours.
 Weak organic acids (such as tannic
acid)
 Sulfur dyes:
 Dark colours
 These are sulfur compounds applied
usually with sodium sulfide.
 Effluent from this dyeing consists of
considerable amount of sulfide.

 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.
 Naphthol dyes :
 Beta-naphthol is first applied to the
fabric, dried and treated with a
developer for coupling and diazotization
after which the colour is formed.
 This is followed be soaping and alkali
treatment.

 Developing dyes :
 Sodium nitrite , acid and beta-naphthol.
 Effluents from this dyeing contains no.
of chemicals
Effluent
 Sources of effluent
 Dyeing and printing
industries
 Textile industries

 Paper and ink

manufacturing industries
 Cosmetics

 Pharmaceuticals

 Food
Properties of effluent before
processing
 Impart colour to water bodies even if
present in small quantity
 Not harmful but undesirable for
aesthetic reason
 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.
 Salts of chromium and aluminium &
iron as mordants in dyes
 Toxic to fish & microbial organisms
 The discharge of heavy metals into
aquatic ecosystems
 Increase in alkalinity of water
 The turbidity and colour along with
oil and scum create an unsighty
appearance.
 The mineral materials, mostly
sodium 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.
 High permanganate value ( 4hrs)
 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.
 Characteristics of Dyeing
wastes
Dyes pH BOD Gallon wastes
per 1000 lb
Aniline - 40 - 55 goods
15,000 -23,000
Black
Basic 6 -7.5 100 - 200 18,000 – 36,000
Developed 5 -10 75 -200 8,900 -25,000
colours
Direct 6.5 - 220 - 600 1,700 – 6,400
7.6
Indigo 5 -10 90 - 1700 600 – 6,000
Naphthol 5 -10 15 - 675 2,300 – 16,800
Sulfur 8 - 10 125 -1,500 2,900 – 25,600

Vats 5 -10 125 – 1,000 – 20,000

1,500
Characteristics of Dyeing Effluent

Sr.No Characteristics Result

. 1. Temperature s 50º C

2. pH value 10.5

3. Phenolphthalein alkalinity (as 13600

CaCO3), mg/l
4. Total alkalinity (as CaCO3), 16100
5. mg/l
Total solids, mg/l 40000

6. Total Suspended solids, mg/l 25200

Sr.No. Characteristics Results
7. Total Dissolved Solids, mg/l 29800

8. Dissolved Fixed Solids, mg/l 24060

9. Permangnate value (4hrs), 376

mg/l
10. Chemical Oxygen Demand, 1490
mg/l
11. Chlorides (as Cl), mg/l 1800

12. Oils & Grease, mg/l 1800

Technologies/
Current Practices
Effluent treatment
comprising primary
(physico-chemical)
and secondary
(biological) system
is in practice. Some
of the units have
also provided
tertiary treatment
and incinerators for
non-biodegradable
waste.
Where H-acid : 1-amino,8-hydroxynaphthalene-3,6-disulphonic acid of the
Requirements
Possibilities for adaptation of
cleaner process options for
reducing the water
consumption and effluent
generation; better
management practices for
segregation and
reuse/recycle of the treated
effluent; effective utilization
of raw materials;
improvement in efficiency of
process; and recovery of by-
products. The effluent
generated from
manufacturing of some
dyes and intermediates such
Gaseous emissions such Properly designed
as SO2, NO2, HCl, and scrubber with recovery
NH3 are generally reuse of scrubbed liquid is
scrubbed. required.
Gypsum, iron sludge and Cleaner process
sludge from ETP are technologies e.g. catalytic
generated as solid hydrogenation, use of
waste. The gypsum and spent acid after nitration
iron sludge can be used for acidification of fusion
in the cement and mass, which can eliminate
pigment industries, The generation of iron and
sludge is either disposed gypsum sludge.
off on land/secured
landfill or sent to other
user industries.
Primary treatment
 Screening
 Equalization

 Neutralization

 Chemical coagulation
Screening

 Screen is a device with opening generally

of uniform size, that is used to retain the
coarse solids found in wastewater.
Removal of debris and solid wastes.
Equalization
 Regulation of flow
rate, also maintains
pH levels of the
system.
Neutralization
Chemical coagulation
Secondary treatment
 Trickling filter
 Activated sludge process
 Aerated lagoon
 Oxidation pond
 Oxidation ditch
 Aerobic Degradation of Dyes

 Anaerobic digestion
 Biosorption
Trickling filter
Activated sludge process
Aerated lagoon
Oxidation pond
 Pond aeration or lake aeration
 Increase in the oxygen
saturation of the water.
 Dissolved oxygen (DO)
 Fish and other aquatic animals
 Aerobic bacteria
 Pond bottoms of organic soils
demand larger amounts of
oxygen.
Oxidation ditch
Oxidation ditch
Aerobic Degradation of
Dyes
 Inefficient treatment

 Resistance to biological oxidation

 Poor adsorption of dyes

 Example : Three anionic dyes i.e CL

reactive violet 15, reactive blue 19
and reactive red 5 were neither
removed nor biodegraded by
activated sewage sludge even after
20 days of incubation.
 Similar findings for sulphonated
water soluble dyes.
Role of fungi and bacteria
 Aerobic oxidation
 Majority of White rot group
 Degrade variety of dyes
 Production of ligninolytic enzymes
 Example: laccase, lignin
peroxidase, manganese peroxidase
and manganese independent
peroxidase.
 Broad substrate specificity
Examples of fungus
 One of the most studied fungus
Phanerochaete chrysosporium has
been shown to degrade large
spectrum of azo, anthraquinone
and triphenylmethane dyes, with
decolorization efficiency of more
than 90%.
 Other examples of white rot fungi
degrading industrially relevant azo
dyes are Geotrichum candidum,
Trametes versicolor, T.modesia, T.
Examples of Bacteria
 Streptomyces species and
Flavobacterium ATCC 39723
 Extracellular peroxidases
 Ability to degrade xenobiotic
compounds including dyestuffs.
 Several other bacteria such as
Citrobacter sp., Kurthia sp.,
Corynebaterium and
Mycobacterium sp., and mixed
culture of Pseudomonas mendocina
and P. alcaligenes degrade
Controversy about aerobic
degradation
 In many reports on the aerobic
metabolism of azo dyes, the
bacterial strains were grown on
complex media aerobically and
incubated under static
conditions in the presence of azo
dyes.
 These static cultures presumably
become rapidly oxygen depleted
and the reactions observed
should be viewed as an
Anaerobic degradation of
dyes
 Anaerobic conditions
 Decolorisation of azo dyes.
 Baughman and Weber (1994)
 Biologically mediated
reductionof azo dyes to the
corresponding amines.
 An upflow anaerobic fixed
film bioreactor
 Bone char as a support
matrix
 A cattle dung slurry as a
source of anaerobic bacteria
 Decolorization of reactive
dyestuff industrial effluent
 Average colour removal and
COD removal efficiency was
found to be 70% and 50%
respectively at organic
 Main advantage of fixed film
bioreactor
 Retention of active biomass in
form of a biofilm attached to a
support
 Without recirculation of biomass
or addition of fresh biomass
 Efficient mass transfer and waste
stabilization.
 Fed batch processes using
Pseudomonas luteola was shown
to effectively decolorize reactive
BIOSORPTION
 A property of certain types of
inactive, dead, microbial
biomass to bind and
concentrate heavy metals from
even very dilute aqueous
solutions 
 Biomass acts as a chemical
substance, as an ion exchanger
of biological origin
 Cell wall structure of certain
algae, fungi and bacteria
 These biomass types can
accumulate in excess of 25% of
their dry weight in deposited
heavy metals:  Pb, Cd, U, Cu, Zn,
even Cr and others
 A complex phenomenon where
the metallic species could be
deposited in the solid biosorbent
through different sorption
processes of ion exchange,
complexation, chelation,
microprecipitation, etc. 
Tertiary treatment
 Reverse osmosis
 Electrodialysis
 Ultrafiltration
 Adsorption on powered
activated carbon
 Membrane filtration
 Nanofiltration
Reverse Osmosis
 Removal of bacteria,
salts, sugars, proteins,
particles, dyes, and
other constituents
 The separation of
ions with reverse
osmosis is aided by
charged particles.
 Dissolved ions that
carry a charge, such
as salts, are more
likely to be removed
by the membrane than
those that are not
charged, such as
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.
 Ultrafiltration
 They are pressure
driven membrane
operations that use
porous membranes
for the removal of
heavy metals. The
main disadvantage
of this process is
the generation of
sludge.
Adsorption on powered
activated carbon
 The most commonly used method of dye
removal by adsorption.
 Effective for adsorbing cationic, mordant
and acid dyes, and to a slightly lesser
extent, dispersed, direct, vat, pigment
and reactive dyes
 Performance depends on the type of
carbon used and the characteristics of
the wastewater.
 Disadvantage: activated carbon is
expensive; it has to be reactivated,
which can result in 10-15% loss of
sorbent.
Membrane filtration

 Clarify, concentrate and separate

dye continuously from effluent
 Resistance to temperature, to an
adverse chemical environment, and
to microbial attack.
 Disadvantages – disposal of the
residue, high capital cost and the
need for membrane replacement.
Nanofiltration
 Nanofiltration membranes are similar to
reverse osmosis membranes in several
respects except the degree of removal of
monovalent ions such as chlorides etc.
 Reverse osmosis membranes provide 90
to 99% removal of ions while
nanofiltration membrane are used for the
selective removal of ions from 50 % to 90
%.
 It depends upon the material and
manufacturing of the membrane.
 Treatment of water from many surface
supplies like wells, rivers or lakes.
Specific Tolerances for Dyestuff
effluents
Sr.N Characteristics
o. Tolerance
1. pH value limits
5.5 to 9.0
2. Suspended solids,mg/l max. 100
3. Dissolved solids (inorganics), 2100
4. mg/l  
Zinc (as Zn) mg/l, max. 5
5. Colour Absent
6. Biochemical Oxygen 30
Demand, mg/l, max.(5 days
at 20 º C)
7. Chemical oxygen demand, 250 
mg/l, max