ECO FRIENDLY

VAT DYEING

By : Karanvir singh
ECO-TEXTILES
A new concept is causing the textile industries to rethink
their strategies:
• Sourcing
• Manufacturing/producing
• Marketing

Eco means:-
A reduction of every negative impact that textiles have on
the environment
In the form of
• Pollution
• Damage to the planet
 TEXTILE PROCESS FLOW

Air pollutants

Inputs
Products
Raw materials
Production
Dyes & Chemicals process Waste
water
Water
Stream
Energy Solid wastes

Change or modify in all areas.

Vat Dyes:
 Vat dyes possess C=O group in their structure and are water
insoluble.
 Non-ionic dyes are reduced to leuco form followed by
conversion to water soluble form in presence of alkali, which in
turn exhibit affinity for cellulosic textiles.
 Vat dyes have mainly anthraquinone (82%) or
indigoid/thioindigoid (9%) structures, with the former having
better fastness properties
 Vat dyes are easier to reoxidize than sulfur dyes and the oxygen
in air is often the agent used. Most vat dyes display high
wash fastness
 The excess alkali remaining on the cloth is neutralized by
scouring.
Representative Anthraquinone vat dye structures
(a) Vat Red 13, (b) Vat Black 27, (c) Vat Orange 2, (d) Vat Blue 4,
(e) Vat Green 1.
VAT DYES
 When the ultimate in wash & boil fastness is required.

 Also used to dye over fibre reactive dyes for multi-layered

dyeing.

YELLOW GREEN
ORANGE OLIVE B
RED BROWN
BLUE NAVY
VIOLET BLACK
REDUCTION VAT DYES
 Leuco potential of vat dyes under standard conditions
lies between -650 and -1000 mV
 Indigo can be vatted around -750mV, but
anthraquinones require higher reduction potential
(around or above -850 mV)
 Reduction of vat dyes is a reversible process
CONVENTIONAL REDUCING AGENTS
 Sodium hydrosulphite
 Copperas method
 Thiourea dioxide
 Sodium borohydride
 SODIUM HYDROSULPHITE
 Sodium hydrosulphite reduces vat dye at Temp of 30-50c,
 Resulting in formation of biphenols(leuco-indigo).

 Leuco indigo,in presence of NaOH gets converted to

mono-phenolate & bi-phenolate forms.

 Na2S2O4 decomposes to liberate nascent hydrogen, which

in turn reduces dye [3].
 Na2S2O4 + 4H2O → 2NaHSO4 + 6H
 Na2S2O4 + 2NaOH → 2Na2SO3 + 2H
 Presence of excess alkali solubilises reduced dye to its Na-
salt.
 Na2S2O4 is very unstable. At the time of reduction of dye,
it gets decomposed thermally, oxidatively and in various
other ways , requiring 2 - 3 times higher amount than
required for reduction of dye .
 Sulphite, Sulphate, thiosulphate and toxic sulphide
heavily contaminate waste water from dyeing plants. An
excessively high sulphate concentration in the effluent
can cause damage to unprotected concrete pipes.

O OH ONa

Na2S2O4 NaOH

O OH ONa
COPPERAS METHOD
 FeSO4 when reacts with Ca(OH)2 produces Fe(OH)2,
which in turn reduces vat dyes and itself gets oxidized to
Fe(OH)3 . The overall reaction is
 FeSO4 + Ca(OH)2 → Fe(OH)2 + CaSO4
 Fe(OH)2 + 2H2O → Fe(OH)3 + 2H ↑

 This method is fallen out due to generation of very bulky

sediment.
 Precipitation of iron on dyed textile makes shade dull &
acid sensitive.
THIOUREA DIOXIDE
 It chemically inert to many reagents,but an irreversible
rearrangement takes place when heated with alkali &
water with formation of formamidine sulphinic acid.
 Sulphoxylic acid which act as active reducing agent.

 It having higher reduction potential valve, due to which

over reduction occur.
 Higher reduction potential value, due to which dyes prone
to over-reduction can not be reduced with it in absence of
inhibitors like glucose, nitrite or hydroxylamine .

H 2N OH H2 N
H 2N
H 2O
CH S C O H2SO2
C SO2
H 2N O H2N
H2N
SODIUM BOROHYDRIDE
 Sodium borohydride is bicomponent reducing
system,mainly developed for pad-steam process.
 Pad steam consist of

 a) Highly alkaline soluntion of Sodium borohydride

 b) Solid consisting of hydroxymethane sulphinic acid

& an accelerator based on nickel-cyanide complex.
 Actual reducer is sodium salt of hydroxymethane
sulphinic acid (Rangolite-c)
 Main problem associated with this is over –reduction.
DISADVANTAGE OF CONVENTIONAL
REDUCING AGENT
 Effluent
 Costs

 Liquor Recycling
ECOFRIENDLY REDUCING AGENTS
 Hydroxyacetone
 Glucose

 Iron(II)Complexs
HYDROXYACETONE

 Hydroxyacetone (CH3 – CO – CH2OH) provides

reduction potential (~ -810mV).
Advantages
 Higher quality dyeing, better ring dyeing effect in dyeing
with indigo.
 Increased productivity.

 Higher dye uptake, less dyestuff in effluent.

 Lower chemical consumption.

GLUCOSE – NAOH SYSTEM

 A combination of Glucose - NaOH provides reduction

potential (–550 to –600mV).
 Indigo requires reduction potential of the reducing bath
around -700mV which can be achieved with this system
at boil.
 Produce reduced indigo baths free from sediments and
highly stable for several hours.
IRON (II) COMPLEXES

 Fe(OH)2 is a strong reducing agent in an alkaline environment , With the

increase in the pH, the reducing effect is more.
 In alkaline conditions it is less soluble and precipitates so it must be
complexed in order to hold the Fe(OH) 2 in solution.
 A stable complex with reducing power is obtained with weaker ligands , e.g.
gluconic acid, diethylene triaminepentacetis acid acid sodium salt (DTPA), 1-
hydroxy ethylidene – 1,1 – diphosphonic acid (HEDP), aminotrimethylene
phosphonic acid.
 There is substantial increase in reduction potential (-765 to -996 mV), even on
addition of agent like Triethanolamine (TEA) as low as 1.5 ml/l
CITRIC ACID/TARTARIC ACID

 Citric acid/Tartaric acid are also used and observed that

the reduction potential is increased in the range of – 873
to -920 mV. It is proposed that for tartaric acid that it
has 4 unshared electron donating sites, 2 sites due to –
OH groups and 2 sites due to –COOH site takes part in
complex formation, 3 molecules of tartaric acid will be
required per molecule of Fe(OH)2.
 Citric acid as a ligand has 4 unshared electron donating sites, 3 due to –
COOH groups and 1 due to –OH groups.
•If –COOH groups take part in complex formation, it will behave like a
tridentate ligand:

If –OH groups take part, citric acid will behave like a monodentate ligand:
GLUCONIC ACID
 Gluconic acid has been found to be effective chelating
agent for iron under alkaline conditions
 Regarding eco-environmental aspect, gluconic acid can
be eliminated in the sewage tank through neutralisation
with alkali; free Fe(OH)2 which due to areation gets
converted to Fe(OH)3 acts as a flocculent and reduces
waste-water load.
 DTPA (Diethylene triaminepentacetic acid sodium salt)
has a good sequestering action on Fe3+ under alkaline
pH.
ELECTROCHEMICAL DYEING
 This method employs as an elecrochemical reversible
system called a redox mediator , as an electron
carrier between electron and the dye.
DYE-BATH CONTAINS