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BLEACHING TEXTILES USING SODIUM CHLORITE

Sodium chlorite is used to bleach textile goods under such conditions that chlorine dioxide, a selective bleaching agent, is generated in-situ. Chlorine dioxide is a non-chlorinating reagent used to obtain a high degree of whiteness on cotton as well as synthetic fibres without degrading them. Using sodium chlorite entails maintaining good control over the pH of the bleaching stage (slightly acidic) and adding an activation agent. Arkema, a major manufacturer of sodium chlorite in Europe, provides technical support for bleaching textile goods under optimum and controlled conditions.
The two main products used by finishers to bleach textiles are hydrogen peroxide and sodium chlorite. Sodium chlorite has been used around the world for over 40 years to bleach textile fibres (100% cellulose fibres or blends of chemical and cellulose fibres). Its advantages over other bleaching agents are many, but its main asset lies in the fact that its reaction selectivity protects textile fibres. Sodium chlorite is also used to partially or completely strip colour from textiles before redyeing them. A process exists that allows desizing and sodium chlorite bleaching to be combined in a single step to boost the bleaching action of sodium chlorite on cotton and cellulose blend fabrics and thereby make preparation more cost-effective.

Bleaching mechanism with sodium chlorite

Sodium chlorite is a light yellow alkaline liquid that is stable at ambient temperature. When broken down by acids, it forms chlorine dioxide (CIO2), a green gas that is readily soluble in water. Chlorite breaks down according to the following mechanism:

5 ClO2- + 4 H+ 4 ClO2+2H
+

4 ClO2 + Cl- + 2 H2O 2 ClO2 + Cl +

-

(I) (II)

ClO3-

+ H2O

Reaction I is always the most important of the two; reaction II is promoted by the drop in pH. Sodium chlorites colour stripping properties used in bleaching textiles are thought to derive from the formation of chlorine dioxide. Bleaching is performed in a weakly acidic aqueous solution with enough sodium chlorite to allow the chlorine dioxide to be absorbed by the textile fibres as it is formed. This process is completely mastered.

Cotton and blends

Semi-continuous processes
In the process called Pad-Roll, sodium chlorite and a high-temperature amylase enzyme are combined in a single bath to strip away both sizing agents and hemicelluloses. It is currently estimated that this enzyme must break down at least 75-85% of them in order for the bleaching process to yield the desired results. The enzyme is barely degraded by the sodium chlorite during the first few minutes of the process. The sizing agents (e.g. starches, polyvinyl alcohols, CMCs, polyacrylates and waxes) are first removed in a nearly neutral or slightly alkaline medium. The enzyme acts by forming watersoluble reaction products in a period of 1-2 minutes. Then, during the reaction process, the pH becomes acidic. The oxygen generated by the chlorite and chlorine dioxide formed in situ destroys the enzyme. The bleaching phase then starts and continues in a hot, acidic medium.

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The impregnation bath is made up of several chemicals. The sodium chlorite (NaClO2) is first combined with an activation agent dissolved in warm water, a non-foaming wetting agent, and a small amount of 35% hydrogen peroxide to control the formation of chlorine dioxide. The high-temperature desizing enzyme, an optical brightener compatible with both the fabric and the chlorite, and the remaining water are then added just before the bath is used. The pH is monitored to ensure that it remains between 6.5 and 8. The bath is then sent to the loading tank. The fabric (in pieces) first passes through the bath in the saturator tank at a speed of 50-100 metres per minute and exits between two squeeze rolls. An impregnation rate of 70-100% is recommended for easier desizing and enhanced whiteness. The fabric is then heated to between 85C and 95 (the C temperature depends on the type of fabric), wound into a box and maintained (at the same temperatures) for 90 minutes to 2 hours. After this, it passes into an industrial washer with at least four compartments through which water flows backwards at a temperature of 95C, then 60 and finally at C ambient temperature. The material is then dyed or finished before being stretched on a frame to dry. QUANTITIES OF CHEMICALS REQUIRED FOR A 1000 LITRE BATH (90% impregnation rate) 50/50 COTTON / POLY BLEND 40-50 4-5 2-5 1-2 2 to 5 67/33 COTTON / POLY BLEND 32-40 3-4 2-5 1-2 2 to 5

COTTON / 100% LINEN COTTON Sodium chlorite 25% solution (litres) Activation agent (kg) Enzyme (kg) Wetting agent (kg) Hydrogen peroxide 35% (litres) 60-80 6-8 2-5 1-2 2 to 5 80-106 6-11 2-5 1-2 2 to 5

100% LINEN 106130 11-19 2-5 1-2 2 to 5

POLYESTER / VISCOSE 30-40 3-4 2-5 1-2 2 to 5

The Pad-Batch process is the same except that the fabric is wrapped in a plastic sheet to prevent evaporation and left to stand at ambient temperature for 15-20 hours.

Batch processes
Batch processes (e.g. kier, package, winch, jet, overflow, and jigger) consist of two steps without any intermediate washing. First, the sizing agents are stripped in a bath containing a non-foaming wetting agent and the high-temperature desizing enzyme. The bath is sent to the processing tank and heated to 80-90 for 10-15 minutes then cooled to 70 C C. Step two consists of bleaching without any intermediate washing. The bath contains the activation agent and the sodium nitrate (corrosion inhibitor) dissolved in warm water, a small amount of 3 35% hydrogen peroxide (2-5 l per m of bath), the 25% sodium chlorite, the amount of formic acid needed to keep the pH between 3.6 and 4, and an optical brightener compatible with the chlorite. It is heated to 95 for 45-60 minutes for cotton/linen o r 115-120 for 30-45 minutes for polyester/cotton C C (temperature ranges for the optical brightener). The bath is then cooled to 80 discharged, and the C, fabric is washed at 95C, then at 65 and finally at ambient temperature. C

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C 10-15 min

Cotton/linen blend

3 whasings

Discharging

Wetting agent Anti-foaming agent Enzyme

Accelerant and sodium nitrate ClO2 H2O2 Formic acid Optical brightener

Batch bleaching with sodium chlorite

QUANTITIES OF CHEMICALS REQUIRED FOR A 1000 LITRE BATH (example for liquor ratios between 1:7 and 1:10) 100% COTTON 0.5-1 1-1.5 3-5 3-5 6-10 1 to 3 1-1.5 (pH 3.6-4) COTTON/LINEN 0.5-1 1 4-6 4-6 8-12 1 to 3 1-1.5 (pH 3.6-4) 50/50 COTTONPOLY BLEND 0.5 0.5-1 2-4 2-4 5-8 1 to 3 1-1.5 (pH 3.6-4) 67/33 COTTONPOLY BLEND 0.5 0.5-1 2-3.5 2-3.5 4-7 1 to 3 1-1.5 (pH 3.6-4)

Wetting agent (kg) Enzyme (kg) Activation agent (kg) Sodium nitrate (kg) 25% solution of sodium chlorite (litres) 35% hydrogen peroxide (litres) 80% formic acid (litres)

Synthetic fibres
These fibres are made by polymerising chemical monomers and extruding them through a die. They are a product of chemical synthesis, hence the name synthetic fibres. In most cases, chemical fibres are white enough to be dyed after being scoured just once (to remove weaving oils). Bleaching may however prove necessary in cases where very light shades of white are desired or if the fabric has turned yellow during heat-setting. Sodium chlorite may be the sole means of bleaching synthetic fibres (in 100% form or blended with other fibres) that are very sensitive to alkaline hydrolysis (used in hydrogen peroxide bleaching). This is particularly the case of polyester fibres, acrylic fibres and, to a lesser extent, polyamides.

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In the case of fibres such as chlorofibres, sodium chlorite yields excellent results without having to exceed the fibres inherent temperature limits (around 50 C). Most of the time these reactions are too slow to be applied in continuous or semi-continuous processes. On the other hand, good results are obtained with a batch processes (kier, jet, overflow). This is particularly true with chlorofibres. QUANTITIES OF CHEMICALS REQUIRED TO BLEACH SYNTHETIC FIBRES (liquor ratio* between 1:7 and 1:10) POLYAMIDE 0.5-1 3-5 3-5 0.75 3-6 POLYESTER 0.5-1 3-5 3-5 1 3-6 ACRYLIC 0.5 3-5 3-5 1 3-6 CHLOROFIBRES 0.5 3-5 3-5 1 3-6

Wetting agent (kg) Accelerant UG45 (kg) Sodium nitrate (kg) Ammonium hydrogen fluoride 25% solution of sodium chlorite (litres) 35% hydrogen peroxide (litres) Acid

0.1-1 l Phosphoric or acetic pH = 3.5 40 then 85-90

0.1-1 l Formic pH = 3.5 90-95

0.1-1 l Formic or phosphoric pH = 3.5 40 then 85-90

0.1-1 l Formic pH = 3.5 50 (Rhovyl)

Temperature ( C)

* Liquor ratio: volume of dyeing bath in litres to the weight of the fibre to be treated in kilograms. After bleaching, polyamides and acrylics must be rinsed with bisulphite in an acidic medium and chlorofibres in an alkaline one.

A less polluting process

Protecting the environment is a major concern throughout the industry, which is attempting to eliminate harmful by-products in bleached goods and reduce pollutants in discharges to a minimum. The objective in bleaching operations is to reduce the formation of polluting by-products, particularly organochlorinated products. Studies have been undertaken to check for the absence of chlorinated organic compounds, notably dioxins, in chlorite-bleached waste cotton. Powerful analysis methods (High Performance Liquid Chromatography coupled with a high-resolution mass spectrometer) have not detected any dioxins (detection threshold of up to 1 ppb). Also, AOX levels measured in wastewater from mills where cotton is bleached with sodium chlorite remain below 0.2 kg per tonne of processed cotton. Good control over the bleaching process allows AOX generation to be decreased even further. By comparison, the legal limit set for paper industries is 1 kg of AOX per tonne of pulp.

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ADVANTAGES OF SODIUM CHLORITE PROCESSES Permanent whiteness. Hulls and aphids are removed from cotton without having to boil it first. Characteristics of cellulose fibres left intact, particularly in the case of linen, viscose, rayon, cell wool and cotton/linen or polyester/viscose blends. Bleaches cotton of mediocre quality, which would be damaged by other methods. Lower weight loss. Maximum whiteness is obtained with synthetic fibres such as polyester in polyester/cotton blends or polyamide in polyamide/cotton blends. Destroys yellowish thermal decomposition products without affecting the polymer structure of synthetic fibres (if bleaching is required). As synthetic fibres are delicate polyamide, polyester, acrylic and chlorofibres in particular sodium chlorite is recommended as a safe and effective bleaching agent. Excellent hydrophilic properties of treated fabrics for uniform dyeing. Less energy, labour, water and time are required when sodium chlorite bleaching is used in steam saturation (J-Box, U-Box, Pad-Roll) and batch mills. The productivity gains are significant and no investment is required. Little chlorine dioxide is released by the combined desizing and bleaching. A ventilation system should nevertheless be installed as a precaution.

OTHER USES OF CHLORITE Sodium chlorite is used in many industries where quality, safety and environmental protection are essential factors the production of chlorine dioxide, a powerful oxidising agent with excellent bactericidal properties. Bleaching of food products, such as starches, flours, fruits and alginates. Bleaching and preservation of leathers and skins. Preservation of food products. Disinfection of flour and preservation of its properties. Treatment of drinking waters. Treatment of industrial process waters. Removal of colour from industrial waste waters.

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Semi-continuous bleaching. Two semi-continuous processes are used for open-width bleaching of cotton fabrics. In the first, called Pad-Roll, the fabric is saturated with a pad (80-100% delivery rate), placed in a steamer at 95-98 and wound in a box i n which steam is injected at a temperature of 95C 98 to keep the air inside moist and warm. The fab ric is spun on its shaft for 1-3 hours. C In the second, called Pad-Batch, the fabric is impregnated with a pad, wound around a shaft at ambient temperature, wrapped in a sheet of plastic to avoid evaporation and spun for 15-20 hours. The fabric then passes into the washer, where it is rinsed in hot then cold water and then dried. Before being dried, it may be neutralised with acetic acid. The advantages to this process are its flexibility and low investment cost.

Pad-Roll process

Pad-Batch process Continuous bleaching. Continuous bleaching lines generally utilise the Pad-Steam process and include continuous desizing and boiling steps. Continuous processes are suitable for large amounts of fabric of the same, or at least similar, quality. The machines used are a saturator (pad), a preheater and a steamer in the shape of a U or J (called a U-box or J-Box). The fabric travels through these chambers for a relatively long period of time (30 minutes on average) in folded (cuttled) rope form (open-width boxes may be used, but they are expensive and bulky) in a 100-102 steam atmosphere. C Several units may be placed side by side so that the fabric may be desized, boiled and bleached once or twice without stopping. A washer is placed at the end to rinse and neutralise the fabric. Hydrogen peroxide is particularly suited to this type of process. Batch bleaching. Batch processes are used for small amounts of fabric. The fabric is bleached in machines called winches with a high liquor ratio (1:20) or jet or overflow machines with a low liquor ratio (1:5 to 1:10). If the latter are used, non-foaming auxiliary agents are necessary on account of the agitation. Jiggers are best for crease-sensitive fabrics (heavy fabrics or those with a high thread count). The liquor ratio is around 1:5. Kiers and beam machines are used more for delicate fabrics such as gauze and bunting as well as knitted fabrics. The liquor ratio is nearly 1:10.

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CENTRE DE RECHERCHE RHNE-ALPES (CRRA) Rue Henri Moissan BP 63 - 69493 Pierre-Benite Cedex FRANCE Water, paper, and textile treatment support team Tel.: +33 (0)4 72 39 80 04 - Fax: +33 (0)4 72 39 80 28
The information given herein is based upon tests conducted by our research centres and backed by selected literature. It does not constitute a guarantee or formal commitment on our part. The extent of our commitment is set out only in our specification sheets. The handling and use of the products as well as the applications thereof remain subject to the regulations defined by the current legislation of each country and shall not give rise to the responsibility of our company.