Indian Journal of Fibre & Textile Research

Vol. 24, March 1999, pp. 58-03

Green technology in textile processing:

Part III - Eco-friendly dyeing of cotton goods
H T Deo· & A I Wasif
Division of Technology of Fibres and Textile Processing, Department of Chemical Technology, University of Mumbai,
Matunga, Mumbai 400 019, India
Received 16 December 1997; revised received and accepted 27 March 1998

A novel eco-friendly dyeing process is described for the dyeing of cotton with reactive, sulphur and vat dyes.
Significant reduction in pollution load in tenns of biochemical oxygen demand (300) and chemical oxygen d~m an d (COD)
is achieved by modified processes (Eco-Process I and Eco-Process II) employing standing bath or by substituting the non-
ecofriendly chemicals with the eco-friendly ones. The reductions achieved in BOD and COD respectively are 7.65% and
17.27% for reactive dyeing, 2.10% and 5.78% for sulphur dyeing and 11.41% and 17.92% for vat dyeing. A considerable
amount of saving in water consumption is also achieved while dyeing with Eco-Process I and Eco-Process II. Eco-Process
II, in particular, results in 38.70%, 50% and 83.33% savings in water consumption during dyeing with reactive, sulphur and
vat dyes respectively. This has also reduced the volume of effluent in a process house.

Keywords: Cotton fabric, Dyeing, Eco-processes, Jaggery, Reactive dyes, Sulphur dyes, Vat dyes

1 Introduction sodium sulphide brings the dye into soluble state;

In the dyeing process, about 30-60 litres of water is
consumed for 1 kg of cloth substrate. This amounts to
about 16% of the total water consumed in a mill' . The
main challenge before the textile industry today is
how to get production at a competitive price by using
safe dyes and chemicals as well as by reducing
pollution treatment costs. There is no single answer to
these questions as it depends upon the various sectors
under consideration, their competence and
multidisciplinary research.
Dyes belonging to azoic, basic (cationic), direct,
disperse and oxidation bases and developers are
termed as affected classes of dyes as some of ~em
find place in the banned lisr. However, none of the
dyes from the remaining classes, viz. reactive, vat,
sulphur and natural, has been banned. Although, these
dyes are unaffected or safe dyes, the practical dyeing
with them is not free from the environmental
problems. . r
With the everincreasing consumption of cotton
textile products, the use of vat, sulphur and reactive
dyes has significantly increased. Dyeing with these
dyes require large quantities of salts to achieve good
exhaustion, which increase the total dissolved solids
(TDS) in e:ffiuents. In sulphur dyeing, the alkaline
I The author has changed his name from H T Lokhande to H T Deo
however, it contributes sulphides in the mill effluene .
Although the natural dyes are eco-friendly, the
metallic mordants used for improved fastness and
better fixation on textiles are not always eco-friendly4.
The dyeing effluent contains unabsorbed dye,
surfactants, auxiliaries and other chemicals which
may increase the pollution load. Noteworthy work for
the removal of dyesS and surfactants6 from effluent
has been reported.
Developments in reactive dyes are the Sumifix
Supra dyes (marketed by Sumitomo Company, Japan)
which are the mixed bifunctional reactive dyes
containing both vinyl. sulphone and monochloro-
triazinyl groups. These dyes overcome the drawbacks
of low degree of exhaustion and fixation, poor
levelness and reproducibility, and low fastness
properties7 • Dawson Intemation;ll patented a process
and the equipment design for fixin dyes or chemicals
using radio frequency energy. In the recent
developments, an electrolytic process is used to
achieve the reduction of sulphur or vat dyes9 .
In continuation of our earlier work to develop new
eco-friendly methods of processing textile goods'O, an
attempt has been made in the present work to dye the
cotton goods with safe dyes, eco-friendly auxiliaries
and chemicals. The work also deals with the reduction
of waste concentration in effluents by reusing dyes
 DEO & WASIF: GREEN TECHNOLOGY IN TEXTILE PROCESSING: PART III
and chemicals recovered from the effluents. The r~use
of low-load effluents has been successfully tried and
has resulted in consiserable saving in water
consumption in the dyeing process.
2 Materials and Methods
2.1 Materials
Cotton hanks (25s) and cambric fabric (warp count,
65 s; weft count, 66s; ends/in.,62; and picks/in.,50)
were used for the study.
Procion Brilliant Red M5B [C.L Reactive Red 2
(18200)], NavKton Jade Green FFB [C.LVat Green I
(59825)] and Sulphur Black BO [C.LSulphur Black I
(53185)] were used.
Sodium hydrosulphite (GR grade), common salt,
sodium hydroxide, sodium carbonate, acetic acid,
calcium chloride, magnesium sulphate, ferric
chloride, mercuric sulphate, silver sulphate, potassium
dichromate and ferrous ammonium sulphate, all of
AnalaR grade;were used.
2.2 Methods
The cotton hanks and cambric fabric were bleached
and mercerized. The cambric fabric was dyed with
reactive and sulphur dyes while the cotton hanks were
dyed with vat dye using the conventional methods as
well as Eco-Processes I and II developed in our
laboratory .
. 2.2.1 Dyeing of Cambric Fabric with Reactive Dye
2.2.1.1 Conventional Method (Exhaust Dyeing)
The bleached mercerized cambric fabric (100 g)
was dyed for t% shade in a laboratory jigger dyeing
machine, keeping the material-to-liquor ratio at 1:4.
The dye fixing agent Sandofix WEI (2 gil) and acetic
acid (I gil) were added to the dyebath and two ends
were given followed by soaping at 80°C using the
conventional method .
2.2.1.2 Eco-Pro,cess I
The bleached mercerized cambric' fabric (100 g)
was dyed for 1% shade in a laboratory jigger dyeing
machine, keeping the material-to-liquor ratio at 1:4.
The following sequence was adopted for the dyeing:
- The fabric was loaded into machine containing
dye fixing agent Sandofix WEI (2 gil) and two
ends were given at room temperature,
- The bath was drained,
- The dissolved dye was added over two ends,
59
- Two more ends were given without making any
additions to the dyebath,
- Predissolved salt (10 gil) was added and one end
given,
- Predissolved salt (10 gil) was added again and
one end given,
- The goods were run for two ends,
- Predissolved sodium carbonate (7.5 gil) was
added and one end given,
- Predissolved sodium carbonate (7.5 gil) was
added again and one end given,
- The goods were given four ends, and
- Bath was drained and soaping was carried out as
per the conventional method,
2.2.1.3 Eco-Process II
The batch to be dyed by the Eco-Process 11 is
preceded by another batch to be dyed following the
conventional method, with a difference that instead of
draining the solutions the same are collected for
recycle and reuse in the Eco-Process II. Thus, the first
batch is dyed by the conventional method f\,llowed by
dyeing of one or more batches. .
In the Eco-Process II, all the sequences were
exactly the same as followed in conventional dyeing.
However, cold wash, dye-fixing treatment, soaping,
hot wash and cold wash were carried out with
recycled water. The wash liquors generated during
cold washing, dye fixing, soaping, hot w.ashing and
cold washing of conventionally-dyed' fabric were
segregated from the dye solution and then treated with
50 mgll lime followed by 150 mgll ferrous sulphate .
The contents were stirred and kept stagnant for 3 h.
The sludge formed was allowed to settle at th e
bottom. The clear supernatant liquor was passed
through a column of activated carbon and the
colourless water was collected and reused in Eco-
Process II .
2.2.2 Dyeing of Cambric Fabric with Sulphur Dye
2.2.2.1 Conventional Method (Exhaust Dyeing)
The bleached mercerised cambric fabric (100 g)
was dyed for 8% shade in a laboratory jigger dyeing
machine, keeping the material-to-liquor ratio at 1:4,
soaped and washed.
2.2.2.2 Eco-Process I
The bleached mercerised cambric fabric ( 100 g)
was dyed for 8% shade in a laboratory jigger dyeing
machine, keeping the material-to-liquor rati o at 1:4 .
60 INDIAN 1. FIBRE TEXT. RES., MARCH 1999
The following sequence was adopted for the dyeing.
- Fabric was loaded into machine containing 10
gil of liquid jaggery (prepared by treating
commercial jaggery with 0.05% citric acid for
20 h) ana 2 gil of sodium carbonate. Two ends
were gIven,
- Predissolved dye was added in two lots over two
ends, gradually raising the temperature to 60°C,
- Fabric was given two more ends at 60°C in the
same bath,
- Common salt (20 gil) was added at 60°C in lots
over two ends,
- Temperature was raised to boil and dyeing
continued at boil for four ends,
- Bath was drained,
- Cold rinsing was done over two ends,
- 2% hydrogen peroxide (100 vol) and little
ammonia were added into the above bath and
oxidation was carried out at 40°C for four ends,
- Bath was drained,
- Soaping was carried out at boil witb I gil soap
and I gil soda ash while giving two ends,
- One end was given in hot water (60°C), and
- One en" was given in cold water.
2.2.2.3 Eco-Process II
The dye liquors and wash ' liquors from
conventional dyeing were segregated form each other
and reused in Bco-Process II. The dye liquor was
replenished with fresh dye, sodium sulphide and
sodium carbonate (each 4.96 g) and used for dyeing a
fresh batch. The wash liquors obtained from
conventional dyeing were treated with 65 mgll lime
and 180 mgll ferrous sulphate. The contents were
stirred and kept stagnant for 3 h. The clear liquor was
passed through a column containing activated carbon
and this treated wash liquor was reused for rinsing,
oxidation, soaping, hot wash and cold wash
treatments in Eco-Process n.
2.2.3 Dyeing of Cotton Hank with Vat Dye
2.2.3.1 Conventional Method
·Cotton hank was dyed in hank dyeing machine,
keeping the material-to-liquor ratio at I :20, following
a standard method of dyeing with vat dyes.
2.2.3.2 Eca-Process I
Cotton hank was dyed in hank dyeing machine,
keeping the material-to-liquor ratio at I :20. The
dyebath was set with one litre of stock vat solution
and one litre of blank vat (10 gil caustic soda and 10
gil sodium hydrosulphite) solution. Well-scoured
cotton hank (I kg) was put into the dye bath at 60°C
and kept as such for 10 min. The hank was then
removed, squeezed and air-oxidised for 5 min. Hank
was put again into the dye bath and dyeing was
continued for 10 min. Once again the hank was air-
oxidised. The above procedure was repeated for the
third time. After oxidation, the hank was rinsed and
then soaped at boil for 20 min in a bath containing 2
gil soap and 2 gil sodium carbonate. This was
followed by hot and cold rinse.
2.2.3.3 Eco-Process II
The total effluent generated during the dyeing of
cotton hank by the conventional method was treated
with lime (100 mgll) and ferrous sulphate (200 mgll).
The contents were stirred and kept stagnant for 3 h.
The clear liquor was passed through a activated
carbon column and the colourless effluent was reused ·
in Eco-Process II for dyeing as we ll as for other
operations. The entire dyeing process was exactly the
same as followed in the conventional method.
2.2.4 Tests
Total solids, suspended solids, total dissolved
solids, biochemical oxygen demand (BOD), chemical
oxygen demand (COD) and pH were determined as
reported earlier lO •
The cotton substrate dyed by the Eco-Process I and
Eco-Process II were compared with those ' dyed by
conventional method for their depth of shade and tone
using the Computerised Colour Matching (CCMI)
System.
The colour changes ,of dyed yam and fabric
samples were measured in tenns- of ern L* a* b*
values with iIIuminants D 65, A and TL 84
respectively at a 10° observer. The work was carried
out on Spectraflash SF 300 system of Datacolor
International, USA.
Wash fastness was determined according to IS04
(BS 1006, C04: 1974) and IS05 (BS 1006 C05 :
1978) methods ll . The colour fastness to day light was
determined according to BS 1006 (1978) method II.
2.2.5 Bulk Trials
Bulk trials for dyeing of cambric fabric with
reactive (Procion Brilliant Red M5B) and sulphur
(Sulphur Black BO) dyes and cotton hanks with V!lt
dye (Navinon Jade Green FFB) using conventional
 DEO & WASIF: GREEN TECHNOLOGY IN TEXTILE PROCESSING : PART III 61

and Eco-Processes I and Il were carried out. The that the treatment of undyed fabric with a dye fixing
cambric fabric was dyed in a jigger, while cotton agent before dyeing can improve the dye uptake.
hanks were dyed in a typ ical yarn dyeing unit. The The KlS and colour difference values of fabric
batch size of cambric fabric was 100 kg while that of samples dyed with Su lphur Black BO by variou s
hanks was 50 kg. The chemicals used were of methods do not show significant difference. Thi s
commercia l grade. indicates that liquid jaggery can give the same degree
o f reduction as obtained w ith sodium sulphide. It
3 Results and Discussion could be good eco-friendly substitute as reduc ing
Table I shows that the fabric sample dyed with agent in sulphur dyeing of cotton.
Procion Brilliant Red M5B by Eco-Process I gives The KlS and colour difference va lues of hanks dyed
hi gher KJS value as compared to the samp le dyed by with Navillon Jade Green FFB show that the sample
the conventional method . The colour difference dyed by Eco-Process I is darker, stronger and more
values also indicate that the sample dyed by Eco- green in comparison to that dyed by the conventional
Process I is darker, stronger and more red as method, indicating that intermediate air oxidation step
compared to the conventionally-dyed sample. Though is more effective in increasing the dye uptake as
the samp le dyed by Eco-Process II is ocomparatively compared to the chemical oxidation. The lower dye
Iighter than the conventionally-dyed samp le, the uptake for the samp le dyed by Eco-Process II may be
co lour difference is negligible. The results Indicate due to the higher co ncentration of dissolved solids in
the recycled water.
The wash and light fastness ratings showed the
Table I -- K/S values of dyed substrates
improved wash fastness for the sample dyed with
Process Dye KlS reactive dye by Eco-Process I. This may be due to the
Co nventional 3.7338 dye t'i xing treatment given in Eco-Process I which
Eco-Process I Procion Brilliant Red 4.7085 helps in reta ining higher amount of dye on the
Eco·· Process II M5B 3.6351 substrate during washing. No change in wash fastness
rating was noticed in case of su lphur and vat dyeings .
Conventional 10.6521
Eco-Process I Sulphur Black BO 11.1 741 The li ght fastness of all the dyed samp les remained
Eco-Process II iO.6672 same.
The waste water generated in dyeing of cotton
Con ve nt iOllal 8.3078
Eco-Process I Navinon Jade Green FFB 9.4044 substrates by different processes was analysed for pH,
Feo-Process II 7.5348 total so lids, total dissolved solids (TDS), suspended

Tab le 2 - Analysis of waste water generated during dyeing of colton suh strates

Process Total solids Total dissolved Suspended so lids Biochemical Chemical oxygen
mg/I solids mg/ I oxygen demand
mg/I demand mg/I
(5 days at 20°C)
mg/I

Shade: I %; pH : 9.0; Procion Brilliant Red M5B

Conven tional 4150 3825 325 170 608
J·:co-Proccss I 3862 355 1 311 147 503
Eco-Process 11 4984 4639 345 178 654
Shade: 8%; pH : 9.2; Sulphur Black BO
Co n vClllional 6394 5874 520 474 1629
Eco-P mcess I 6103 5610 493 464 1535
Eco-Pmcess li 751 I 6975 536 489 1730
Shade: t %; pH : 10.5; Navinon Jade Green FFB
Co nveni iom1.! 4685 4237 448 219 806
Eco-Process I 4262 3793 469 194 662
I·:co ·l'roccs;; 11 56 12 5135 477 230 874
62 INDIA N J. FIBRE TEXT. RES. , MARCH 1999

so lids, BOD and COD and the results are given in the Eco-Process II effluent as compared to that for the
Table 2. The effluent generated in dyeing of cambric conventional method effluent.
fabric with reactive dye by the conventional method Fairly large volume of effluent is generated in the
shows alkaline pH and high TOS contents which may dyeing of cotton hanks with vat dye. The effluent
be due to the usage of large quantity of salt in dyeing generated by the conventional method shows higher
for exhaustion . The BOD and CO O values for the values of pH, total solids, BOD and COD. However,
effluents generated by the conve nti onal method of in the Eco-Process I, the chemical oxidation with non-
dyeing are 170 mg/l and 608 mg/ l res pectively, which ecofriendly dichromate-acetic acid system has been
are quite high. Therefore, certain modifications replaced by the intermediate air ox idation process.
become essential in the existing process . In the Eco- Hence, Eco-Process I effluent shows lower values of
Process I, the use of acetic acid, which contributes to BOD and COD. The Eco-Process II shows some
hi gh BOD, is avoided. Further, more exhaustion of increase in BOD and COD values but achieves good
the dye on the fabric is al so achieved, thereby amount of savings in water consumpt ion.
reducing the concentration of residual dye in the Table 3 shows savings in water consumption \11
effluent. Therefore, Eco-Process I shows lower values
of BOD and COD (147 mg/I and 503 mg/l Table 3 - Water co nsumpt ion in dye ing
respecti ve ly) for th e effluent as compared to that Amount of water, litre
shown by the co nve nti onal meth od. Due to the Step Co nven- Eco-P rocess Eco-Process
recycling of wash liquors from conventional dyeing, ti onal I II
pro ce~s
hi gher values 'Of tota l solids, total di ssolved solids,
Dye: Procion Brilliant Red MSB
BOD and COD are observed for Eco-Process II
effluent. However, due to the recycling of wash Hot wash before dye ing 400 Nil 400
Dyeing 150 150 150
liquors, not only the saving in water consumption but Co ld wash afte r dye ing 400 N il 400'
al so the reduction in volume and average pollution Soaping 400 400 400'
load of the effluent are achieved. Hot wash after soaping 400 400 400'
Final cold wash 400 400 400
The effluent from co nventional dyeing of cambric Total water consumpti on 2150 13)(1 950
fabric with sulphur dye shows alkaline pH, very high Total savings per batch of 800 1200 b
100 kg fabric
va lues of total solids, BOD and COD. The effluent
Saving in monetary terms 37.20% 38.70%
al so contains more harmful chromium. By
substituting sodium sulphide, which contributes to the Dye: Sulphur Black BO
sulphid e io ns in the effluent, with eco-friendly liquid Dye ing 200 200 200
jaggery in Eco-Process I, substantial reduction of the Rin sing after dye ing 400 400 400'
Soaping 400 400 400'
sulphid e content in the effluent is achieved .
Hot wash 400 400 400'
Moreover, the foul smell of sodium sulphide is also Cold wash 400 400 400
e liminated . Further, non-ecofriendly chemicals like Total water co nsumpti on 1800 1800 600
potass ium dichromate, acetic acid, etc. used in the Total savings per batch N il 1200 b
conve nti o na l method have been substituted with the of 100 kg fabri c
Saving in monetary terms N il 50%
eco-friend ly hydrogen peroxide. As a result, the
e fflu ent from Eco-Process I shows lower values of Dye: Navinon J ade Green F F'B
tota l so lids, BOD and COD than shown by the Hot wash befo re dyei ng 1000 1000 1000'
efflu ent fro m th e conventional method . The leftover Dyei ng 1000 1000 1000'
dyebath used in the conventional method was Rin sing afte r dye ing 500 500 500'
Soaping 1000 1000 1000'
replen ished with fresh am ounts of dye, sodium
I-lot was h 1000 1000 1000'
ca rbonate, sodium sulphide and salt in Eco-Process II Co ld wash 1000 1000 500
and the dye in g of th e second batch was carried out. Total water consumpti on 5500 5500 500
S imilarl y, th e wash liqu ors ge nerated in post-dyeing To tal sav ings per batch o f N il 5000 b
ope rati ons of conventi ona l meth od are put to reu se, 100 kg fab ri c
Sav in g in monetary term s N il 83 .33%
after givin g suitabl e treatments, for washing, soaping
and ox id ati on in Eco-Process II. Slightly hi gher • Recycled water
va lues of tota l so lids, BOD and COD are observed for bFor two batch es (o ne each by conventi onal and Eco-Process II )
 DEO & WASIF : GREEN TECHNOLOGY IN TEXTILE PROCESSING : PART III
dyeing of cambric fabrics with Procion Brilliant Red
M5B I, and Sulphur Black BO using Eco-Processes I
and II instead of the conventional one. For reactive
dyeing, Eco-Process I results in saving of 800 litres
water per batch of 100 kg fabric and Eco-Process II
results in saving of 1200 litres water per batch. In
monetary terms, the savings obtained per batch in
Eco-Process I and Eco-Process II are 37.20% and
38.70% respectively. In sulphur dyeing, Eco-Process I
does not give any saving in water consumption, but
Eco-Process II results in saving of 1200 litres water
per batch. In monetary terms, the saving per batch is
50%.
In hank dyeing with Navinon Jade Green FFB, the
Eco-Process II results in saving of 5000 litres water
per batch of 100 kg fabric. In monetary terms, the
saving per batch is of the order of as high as 83.33%.
63
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