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Processing, Dyeing & Finishing

Enzymatic application for bleach cleanup

By using enzyme for bleach cleanup one can get the benefits from the environmental point as well as from the economical
point of view like reduced water, energy and chemicals consumption, assert M Subramanian Senthil Kannan and R
Nithyanandan.

The preparatory process is the first step towards final quality. The bleaching of textile fibres with
hydrogen peroxide is certainly the most popular process today, because of hydrogen peroxide, an
oxidizing agent that has diversified uses. It can be implemented under very different conditions
of processing according to fibres and manufacturing processes. Its role is particularly appreciated
in the bleaching of natural fibres, but can be used, under certain conditions, for the bleaching of
a majority of synthetic fibres alone or in mixtures, In the form of an aqueous solution, it is easy
to store and use. It is particularly well adapted on the continuous lines; Cotton bleached with
hydrogen peroxide has a stable white, a soft touch and absorbency well suited for dyeing.

The traditional method of removing the residual hydrogen peroxide is by rinsing the fabric a
number of times with water. Alternatively, a mild reducing agent can be used to neutralise the
bleach. In either case, large amounts of water (up to 40 litres per kg of fabric) are required for
rinsing the fabric to remove residual hydrogen peroxide. Since any residual hydrogen peroxide
has to be removed to avoid problems in subsequent dyeing process.

The presence of hydrogen peroxide in the dye bath can cause decolourisation of reactive dyes,
which are sensitive to oxidization. It is already known that even minor modification of the dye
molecule can result in colour loss. Even small colour changes can render the dyed fabric
commercially unacceptable due to the stringent contemporary quality requirements.

These demands, which at first glance may appear contradictory, ie, to reduce water consumption
by shortening or eliminating the washing cycle after bleaching whilst at the same time ensuring
good reproducibility of dyeing, may be met by adopting modern biotechnology, that is enzymes.

Enzymes

Enzymes are used in the textile industry because, they accelerate reactions, act only on specific
substrates, operate under mild conditions, are safe and easy to control, can replace harsh
chemicals and are biologically degradable, ie, biodegradable.

Catalase is an enzyme widely distributed in nature and well known for its ability to catalyse the
conversion of hydrogen peroxide to water and gaseous oxygen. An example for the catalytic
power of enzymes is the activity of catalase; one molecule of this enzyme can convert 5x106, ie,
five million molecules of hydrogen peroxide to water and oxygen in one minute! This enzyme will
occur in almost all aerobically respiring organism and serves to protect the cells from the toxic effects of hydrogen peroxide.
It has found numerous applications in food science, industrial food production, medical and analytical fields.

Commercial products containing catalase for textile applications are also available. These have been used to decompose
residual hydrogen peroxide in fabric prior to dyeing, and are normally applied after draining the bleaching bath and refilling
it with fresh water. However, limitations are imposed by the low temperature and alkali stability of the enzyme.

Bleach cleanup

In conventional method generally, bleaching of cellulose fibres with hydrogen peroxide is optimum at a pH of 10, 5 to 11, at
a temperature between 80 and 100C, and for a contact time between 45 - 60 minutes. After completion of the process the
bleached liquor was drained out, then the fabric was rinsed with water a number of times to remove the H 2 O 2 from the
bleached fabric. Alternatively, a mild reducing agent can be used to neutralise the bleach. In either case, large amount of
water (up to 40 litres per kg of fabric) are required for rinsing, which result in discharge of a large volume of wastewater.

An enzyme can be used to replace a chemical agent (such as thiosulfate) in bleach neutralisation leading to reduction in
water and energy consumption. Enzymes provide a more convenient alternative because they are easier and quicker to use.
Compared with the traditional clean-up method, the enzymatic process results in reduced water consumption and reduced
energy consumption.

Enzyme reaction

The enzyme specifically breaks down hydrogen peroxide into non-active oxygen and water under mild temperature
conditions.
Catalase
2 H 2 O 2 ----------------> O 2 + 2 H 2 O
The activity of the enzyme is 10 KCIU/g . One KCIU activity unit (Kilo Catalase International Unit) is the amount of enzyme

that breaks down one mill mole of hydrogen peroxide per minute under standard conditions (25o C, pH 7.0, 10 mill mole
H 2 O 2 ) [2] .

Under industrial conditions, Terminox Ultra takes 10 to 15 minutes to break down the hydrogen peroxide completely and
then the dye can be added.

The various advantages of using the enzyme are that there is no:

Adverse effect on dyestuffs

Need for heating

Need for rinsing prior to dyeing

Risk of harmful overdosing

Formation of byproducts in wastewater

Enzymatic bleach cleanup

The following process, a simple and easy method for batch processing in, eg, yarn dyeing equipment, jet dyers and winches
is as follows:

Drain the bleaching liquor -- Fill with fresh cold water -- Add 0.5-1.0 g/l Terminox - Check hydrogen peroxide after 10 -15
min - Refill with fresh water and start dyeing. The rinsing step is not required when using the enzyme because the bleaching
agent is decomposed and the residues of the enzyme have no effect on textile fibres or dyestuffs. In cases where the fabric
is very dirty it is recommended to include a rinsing step between bleaching and dyeing. A catalase used for bleach cleanup
in the textile industry ensures complete removal of excess H 2 O 2 without requiring the traditional extra rinsing steps. The

optimum temperature is between 30 C to 50 C and the optimum pH is 4.0 - 9. Better colour shade and fastness values can
be achieved in enzymatic processes as that of in the conventional process.

Temperature profile of the catalase activity:

The activity of the enzyme (Terminox ultra) against temperature and pH is plotted in the Figures 1 and 2.

The activity (mol/min) of the enzyme, terminox ultra, which was used in this project
against the temperature is plotted in the Figure 1. This catalase activity was measured by
phosphate buffer (incubation time 1 hour at the corresponding pH). From the graph it is
clearly known that the enzyme is highly active at lower temperature. When the
temperature was increased the catalase activity was reducing rapidly, at a certain
temperature, above at 70 C it was coming down.

After bleaching the bleached bath is to be kept to cool to room temperature and then the
enzyme can be added in that. One can add the enzyme at 60 C but due to high alkalinity
of the bleaching solution the enzyme was deactivated. So adding the enzyme at 30 C in the bleaching bath gives better
results than adding it at higher temperature.

PH profile of the enzyme activity:

The activity (mol/min) of the enzyme, terminox ultra against the PH is plotted in the Figure
2.

This catalase activity was measured by phosphate buffer (incubation time 1 hour at the
30 C temperature). From the graph it is clearly known that the enzyme is highly active at
pH level near to neutral condition. When the alkalinity was increased the catalase activity was reducing rapidly, and at a
certain pH level (above 11) it was coming down.

Normally, the pH value after bleaching comes to around 9 - 11. The pH level after bleaching is highly dependent on the
additives we are using during bleaching, eg, sodium silicate and sodium hydroxide, etc. Conventional enzyme used for bleach
cleanup is stable in lower pH level; Thereby the enzyme was added in the next bath, neutralised with acetic acid in the fresh
water.

This terminox ultra enzyme was highly active at 9 - 10.5 pH level, so the enzyme can be added directly in to the bleached
bath without any addition of acetic acid (for reducing the pH level). Due to the high alkali stability of the enzyme, the
hydrogen peroxide in the bleaching bath was completely destroyed at the pH level of 10.5.

The amount of enzymes need for reducing hydrogen peroxide is found by the following trials.

Enzymes gms per liter

Enzyme reduction process on the residual H 2 O 2 was tested, though no hydrogen peroxide content was detected in the
bleached bath at 4 g/l of enzyme concentration.

After hydrogen peroxide bleaching the bath had cooled to 30 C, then the 4 g/l catalase
enzymes was added in to the bleached bath and the bath kept for 20 - 30 min. After this
process, the hydrogen peroxide content, remaining in the catalase treated bleaching bath
had been evaluated, though no residual hydrogen peroxide contents were detected. The
result shows that the catalase enzyme can be efficiently used to reduce the hydrogen
peroxide instead of using other reducing agent like thiosulphite, etc.

After bleach cleanup the reactive dyeing was carried out in the catalase treated bleach
bath. The bleaching bath formulation and the enzyme caused unacceptable colour changes
in the dyed fabric when dyeing was conducted in the catalase treated bleaching bath. The unacceptable colour changes in
the dyed fabric could be reduced significantly and a good dyeing result can be achieved by varying the parameters in the
dyeing process like bath temperature, salt, dye & alkali concentrations. However the overall influence of these parameters
on the colour difference of the dyed fabric is by the complex action. Selecting the optimum proportion between each of these
parameters could be the key for successful dyeing in the catalase treated bleaching bath.

Conclusion

The textile industry was identified as a key sector where opportunities available from adapting biotechnology are high, but
current awareness of biotechnology is low. In textile processing the enzyme can be successfully used for several processes
from preparatory to finishing. Using enzyme for bleach cleanup one can get the benefits from the environmental point as
well as from the economical point of view like reduced water, energy and chemicals consumption. From these advantages
the savings in water charges are the most significant. Instead of 8 litres per kg of fabric in conventional rinsing, no additional
water is required for bleach cleanup in the enzymatic method.

References

1. Gitte Pedersen: Enzymatic Treatment of Residual Bleach in Cotton Dyeing, Draft UNEP Cleaner Production Worldwide
Publication, 1994.

2. Annelies den Braber, TME, Institute for Applied Environmental Economics, 2511 BJ The Hague, Netherlands.

3. Skjern Tricotage-Farveri A/S Farverivej 1, DK-6900 Skjern, Denmark.

4. Dr T Ramachandran and Dr A Venkatachalam: Improved Energy Conservation in Textile Wet Processing, PSG College
of Technology, Coimbatore.

5. Dr Nikhil and Dr Anita Nishkam: Enzyme in Wet Processing, The Indian Textile Journal, Feb 2003.

6. Dr V A Shenai: Pre-treatment Developments, The Indian Textile Journal, June 2003.

7. Dr Usha Sayed: Novel Trends in Textile Preparatory Process, Colourage, Feb 2002.

8. Pardeshi and Sujita: Recent Developments in Wet Processing, The Indian Textile Journal, Jan 2003/29.

9. Niels P Jensen: Catalase Enzyme, Textile Chemist & Colourist & American Dyestuff Reporter,Vol 32, May 2000.

Note: For detailed version of this article please refer the print version of The Indian Textile Journal February
2008 issue.

M Subramanian Senthil Kannan


Department of Textile Technology,
PSG College of Technology, Coimbatore,
Tamil Nadu 641 004.

R Nithyanandan
Department of Textile Technology,
PSG College of Technology, Coimbatore,
Tamil Nadu 641 004.

published February , 2008

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