Improved Sustainability of Cotton Sulfur

Dyeing by Pad-Ox Processes

Awais Khatri, Abdul Salam, Fahmina Absarullah, and Rafia Anwar

Abstract Sulfur dyeing of cotton textiles is widely practiced in textile industry for
producing inexpensive black, navy, brown, olive, and green shades in medium to
heavy depths. As a part of sulfur dyeing process, intensive rinsing is carried out to
remove unfixed dyes after dyeing. The unfixed dyes produce high sulfide content
and hence undesirable levels of oxygen demands to the effluent. Clariant Ltd.
introduced eco-sustainable processes for sulfur dyeing, generally known as pad-
ox, using Diresul RDT sulfur dyes. This chapter presents a study on comparing
effluent quality, ultimate color yield and colorfastness, and cost of pad-ox dyeing
methods with the conventional pad-steam dyeing. The study showed that the pad-ox
processes produce reduced oxygen demands of effluent with higher color yield and
acceptable colorfastness. Interestingly, a review on water and energy consumption
showed that pad-ox dyeings are cheaper than the conventional dyeing.

Keywords Cotton • Pad-ox processes • Sulfur dyeing • Sustainable

1 Introduction

Sulfur dyes are the most economical dyes ever introduced for cellulosics, especially
cotton textiles. They are widely used in the textile industry for dyeing cotton
to produce inexpensive black, navy, brown, olive, and green shades in medium to
heavy depths [1–4]. However, intensive rinsing is required for removing unfixed
dyes after dyeing to achieve acceptable colorfastness. The rinsing generates large
amount of drainage water with high sulfide content, which creates undesirable
levels of oxygen demands to the dyeing effluent [2, 3, 5–7].

A. Khatri (*)
Department of Textile Engineering, Mehran University of Engineering and Technology,
Jamshoro 76062, Pakistan
e-mail: ask_textile@yahoo.com

M.A. Uqaili and K. Harijan (eds.), Energy, Environment and Sustainable Development, 229
DOI 10.1007/978-3-7091-0109-4_23, # Springer-Verlag/Wien 2012
230 A. Khatri et al.

Sulfur dyes are chemically reduced using sodium sulfide or sodium hydrosulfite
to produce their soluble leuco form before application. Immediately after applica-
tion of leuco dyes via aqueous medium, the substrate is subjected to oxidation using
a mild oxidant such as sodium perborate. Thus, the dyes are converted to their
original insoluble form and trapped within the fiber polymer of the substrate
[2–4, 8]. The conventional reduction and oxidation processes create sustainability
problem to the effluent. The ecological alternatives to the reduction and oxidation
processes have been well reported [8–10]. The ecology in terms of sulfide content
and economy in terms of the amount of water and energy consumption remained
major concerns in sulfur dyeing of cotton.
Clariant Ltd. [11, 12] introduced pad-ox processes as the eco-sustainable
and economic way of sulfur dyeing of cotton. The new processes propose 100%
fixation of the dyes to substrate; hence, no dye is drained in rinsing. This work
was undertaken in collaboration with Clariant Pakistan Ltd. to present practical
advantages of continuous pad-ox dyeing methods over conventional pad-steam
dyeing. Three ways of new dyeing technique, pad-ox, pad-dry-ox, and pad-steam-
ox, were studied against pad-steam dyeing.

2 Experimental

2.1 Materials

A mill scoured, bleached, and mercerized cotton woven fabric (250 g/m2, twill) was
used for all dyeings.
Diresul RDT sulfur dyes (Clariant), Brown RDT-GS, Navy RDT-GF, and Black
RDT were used. The Clariant dyeing auxiliaries were Reducer RDT, Penetrant
EHA, Landiquest 1097N, Diresul Oxidant BRI, Indosol E-50, Leveler F, and Sirrix
AK. The sodium hydroxide, sodium hydrosulfite, sodium carbonate, sodium sul-
fate, and acetic acid were analytical grade.

2.2 Methods

Clariant-recommended methods were adopted. All fabrics were dyed to a heavy

color depth of 120 g/l. Concentrations of dyeing auxiliaries are given in Table 1.

2.2.1 Pad-Steam Dyeing

Fabric samples were padded in dyeing solution (70% liquor pick-up, ambient tem-
perature, Rapid P-B1 horizontal padder), steamed (wet-temperature of 101–102
C,
Improved Sustainability of Cotton Sulfur Dyeing by Pad-Ox Processes 231

Table 1 Concentrations of dyeing auxiliaries

Concentration (g/l)
Auxiliaries Pad-steam Pad-ox Pad-dry-ox Pad-steam-ox
Padding solution
Reducer RDT 25 15 15 15
Sodium hydroxide 50% 20 15 15 15
Penetrant EH 2 3 3 6
Landiquest1097N – 3 3 3
Sirrix AK liquid 2 – – –
Sodium hydrosulfite 2 – – –
Oxidation solution
Diresul oxidant BRI 6 25 25 25
Acetic acid 80% 4 25 25 25
Indosol E-50 – 23 23 23
Leveler F – 5 5 5
Sodium sulfate – 30 30 30
Soaping solution
Sirrix AK liquid 2 – – –
Sodium carbonate 2 – – –

Table 2 Initial rinsing Black Brown and navy

conditions after steaming
Rinsing Temperature Time Temperature Time
steps (
C) (s) (
C) (s)
1 50 60 40 60
2 60 60 50 60
3 70 60 60 60

100% moisture, 60 s, Rapid H-TS-3 laboratory steamer), rinsed as per Table 2,

oxidized (70
C, 60 s), rinsed (60
C, 180 s), soaped (90
C, 180 s), rinsed (60
C,
180 s), hydro-extracted (Haier HWS60-40 spin dryer), and finally dried (ambient
air). Rinsings, oxidation, and soaping were carried out on a Rapid HT dyeing
machine.

2.2.2 Pad-Ox Dyeing

Fabric samples were padded (60
C), subjected to ambient airing (60 s), oxidized
(75
C, pH of 4–4.5, 60 s), rinsed (75
C, 180 s), hydro-extracted, and finally dried
(ambient air).

2.2.3 Pad-Dry-Ox Dyeing

Fabric samples were padded (60
C), dried (100
C, 60 s, Thermostatic GZX-GF-
101 drying box), oxidized (75
C, pH of 4–4.5, 60 s), rinsed (75
C, 180 s), hydro-
extracted, and finally dried (ambient air).
232 A. Khatri et al.

2.2.4 Pad-Steam-Ox Dyeing

Fabric samples were padded (60
C), steamed (wet-temperature of 101–102
C,

100% moisture, 60 s), oxidized (75
C, pH of 4–4.5, 60 s), rinsed (75
C, 180 s),
hydro-extracted, and finally dried (ambient air).

2.3 Measurements and Analysis

2.3.1 Color Yield

Color yield (K/S) is used as a measure of the amount of dye fixed on colored
textiles. K/S value is determined from surface reflectance (R) of the substrate as
K/S ¼ (1 – R)2/2R. It was determined using a Datacolor 600 spectrophotometer.

2.3.2 Colorfastness Testing

Dyed and printed textiles tend to fade in color during use because of color loss by
rubbing, washing/laundering, and/or exposure to light. The fading is tested by
standard colorfastness tests, the results of which reflect the quality of colored textile
material. The dyed fabric samples dyed were tested for colorfastness to rubbing
(ISO 105-X12), to washing (ISO 105-C03), and to light (ISO 105-B02). In order to
compare colorfastness properties, color of samples dyed by new processes was
matched to that of the conventionally dyed samples.

2.3.3 Effluent Testing

Chemical oxygen demand (COD) and biochemical oxygen demand (BOD) are
widely used parameters for testing sustainability of the effluent water. Draining
water was collected during washing-off of fabrics dyed with Diresul Black RDT
and tested for COD (HACH) and BOD (HACH).

3 Results and Discussion

The ecology and economy are key advantages offered by pad-ox sulfur dyeing
techniques. The new processes produce no dye in the effluent, thus reducing the
ecological threat. In addition, the new processes have only one short rinsing instead
of three thorough rinsings, thus reducing a lot of water and energy consumption
[11, 12]. The results obtained for comparative color yield, colorfastness, and
Improved Sustainability of Cotton Sulfur Dyeing by Pad-Ox Processes 233

effluent quality are discussed in the following sections. A review on water and
energy consumption is also presented.

3.1 Color Yield

Figure 1 shows that the pad-ox processes produced higher color yields than pad-
steam process. This should be expected since the new processes are claimed to
provide 100% dye fixation to the substrate. Pad-ox process gave a significant
increase in color yield that was even better than other new processes.

3.2 Colorfastness

As given in Table 3, pad-ox and pad-dry-ox produced less rubbing fastness than
pad-steam. This may be because fabric is subjected to dry air after padding, which
results in poorer rubbing fastness [2, 3]. Pad-steam-ox produced similar rubbing

14 Pad-steam
Pad-ox
12
Pad-dry-ox
10 Pad-steam-ox

8
K/S

2
Fig. 1 Color yields obtained
by pad-steam and new 0
processes Brown Navy Black

Table 3 Colorfastness results (gray scale rating for colorfastness to rubbing and washing; Br ¼
brown, N ¼ navy, Bl ¼ black)
Colorfastness to rubbing Colorfastness to washing Colorfastness to light
Dry Wet Color change Staining Blue wool ref.
Process Br N Bl Br N Bl Br N Bl Br N Bl Br N Bl
Pad-steam 4.5 4.5 4 3.5 3.5 2.5 4 4.5 4 4.5 4.5 4 7 6 6.5
Pad-ox 4.5 4 3.5 2 2 1.5 4.5 4 4.5 4.5 4 4.5 6 6 7
Pad-dry-ox 4 3.5 4.5 3 2.5 3 4.5 4.5 4.5 4.5 4.5 4.5 7 7.5 7.5
Pad-steam-ox 4.5 4.5 4.5 3 3.5 3 4.5 4 4.5 5 5 4.5 7 6 7
234 A. Khatri et al.

Table 4 Effluent testing Process COD (ppm) BOD (ppm)

results
Pad-steam 134 63
Pad-ox 114 53
Pad-dry-ox 108 48
Pad-steam-ox 119 51

fastness to pad-steam. Colorfastness to washing and to light produced by the new

processes is generally similar to that produced by pad-steam process. In fact, pad-
dry-ox and pad-steam-ox produced slightly better washing and light fastness.

3.3 Effluent Quality

Effluent testing results for black are given in Table 4. Note the new processes
provide a 10–18% reduction in COD and 15–23% in BOD. The pad-dry-ox gave
better reduction in oxygen demands among the three new processes. These are
encouraging results for ecological benefit and may be for economic benefit in terms
of costs of effluent purification or load-based penalties on more polluted effluent.
The new processes still produce certain levels of COD and BOD. This is because
of the use of conventional reduction and oxidation chemicals. A considerable
reduction in the level of oxygen demands may be expected by utilizing ecology
alternatives for reduction and oxidation treatments in pad-ox processes [8–10].
The color yield, colorfastness, and effluent quality conclusions could be useful for
the selection of a new process having known the need of a customer or the end use.

3.4 Water and Energy Consumption

Water consumption has a considerable influence on the economy of any process.

Two rinsings and soaping steps are eliminated in the new processes if compared
with pad-steam process. Therefore, the new processes save around 90% of the
amount of water consumed in conventional dyeing [11, 12]. Further, the energy
consumption in terms of power and steam is minimized. The cost on soaping
chemicals is also saved. The pad-ox is cheaper than pad-dry-ox and pad-steam-ox
because drying and steaming consume a significant amount of energy.

4 Conclusions

The new pad-ox processes for dyeing cotton with sulfur dyes are effective for
reducing effluent load and the cost. The processes produced higher color yields and
acceptable colorfastness. Pad-ox processes generally resulted around 15–23%
Improved Sustainability of Cotton Sulfur Dyeing by Pad-Ox Processes 235

reduction in oxygen demands of the effluent. The reduced effluent load, around
90% reduction in the amount of water use, considerable reduction in the amount
of energy consumption, and not using soaping chemicals offer a great cost and
sustainability advantage to dye-houses. Further, it is expected that more reduction
in the effluent load can be obtained if pad-ox processes are carried out using eco-
sustainable chemicals for reduction and oxidation treatments.

Acknowledgments We gratefully acknowledge the support and assistance of Dr. Bilal Haleem,
Mr. Hadi Raza Lakhani, Mr. Kamran Khatri and Mr. Amir Shamsi, Clariant Pakistan Ltd. Karachi.

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