De-sizing Process and its types

De-sizing Process
A process carried out to remove the sizing material (like starch) from the cloth.

Objective of De-sizing

1. To eliminate the water repellent nature of sized cloth.

2. To increase the absorbency.
3. To reduce the consumption of chemicals in subsequent process.

Importance of De-sizing

The importance of de-sizing is mainly because of water repellent nature

of “Sizing materials”. So, it is important to remove the size material before
conducting any coloration or finishing process.

Enzymatic desizing

What are enzymes?

Name
 Greek, meaning “In Yeast”

Nature
 Bio-catalyst (proteins)

Structure
 Usually large & complicated

Properties
 Specific action
 Thermo ability
 Low energy of activation
 Narrow working pH arrange

Classification
 According to origin
 According to action
 According to structure
 According to working temperature
Sources of Amylases
 Malt
 Bacteria
 Pancreas

Requirements of desizing:

 Desizing materials
 Desizing methods
 Desizing machine

Desizing processes
Desizing, irrespective of what the desizing agent is, involves impregnation of the fabric with the
desizing agent, allowing the desizing agent to degrade or solubilise the size material, and finally
to wash out the degradation products. The major desizing processes are:

 Enzymatic desizing of starches on cotton fabrics

 Oxidative desizing
 Acid desizing
 Removal of water-soluble size

Enzymatic desizing
Enzymatic desizing is the most widely used desizing process of degrading starch size on cotton
fabrics using enzymes. Enzymes are complex organic, soluble bio-catalysts, formed by living
organisms that catalyze chemical reaction in biological processes. Enzymes are quite specific in
their action on a particular substance. A small quantity of enzyme is able to decompose a large
quantity of the substance it acts upon..
Amylases is the enzyme that hydrolyses and reduce the molecular weight of amylose and
amylopectin molecules in starch, making it water soluble enough to be washed off the fabric.
Effect of PH and Temperature on enzyme desizing
Effective enzymatic desizing require strict control of pH, temperature, water hardness and
electrolyte addition Activity of enzymes increase with temperature; however, above a
critical temperature, enzymes are deactivated. The effectiveness of enzymes exhibit a
maximum at certain temperatures, usually 40 -75 0C. Bacterial enzymes are the most
thermally stable and can be used up to 100 0C under special stabilizing conditions.
Certain salts increase the activity of specific enzymes. Pancreatic amylase is ineffective
without the addition of salt. A combination of sodium chloride
Exhaust Process
Enzyme 4 g/l
NaCl 4 g/l
Wetting Agent 1 g/l
Continuous Process

1. Saturate fabric with a solution containing:

Bacterial Amylase 0.8 - 1.0 %

Wetting agent 0.1 - 0.2 %
Sodium Chloride 10 %

2. Hold:

Open-width Range: Steam 1 to 2 minutes at 200 to 212 0F.

Rope Range: Store in J Box for 20 to 30 minutes at 170 to 180 0F. or
over night at room temperature.
3. Thoroughly rinse with hot water, 175 0F or hotter.
Oxidative desizing
In oxidative desizing, the risk of damage to the cellulose fiber is very high, and its use for
desizing is very rare. Oxidative desizing uses potassium or sodium persulfate or sodium bromite
as an oxidizing agent.
Acid desizing
Cold solutions of dilute sulphuric or hydrochloric acids are used to hydrolyze the starch,
however, this has the disadvantage of damaging cellulose fiber in cotton fabrics.
Removal of water-soluble sizes
Fabrics containing water soluble sizes can be desized by washing using hot water, perhaps
containing wetting agents (surfactants) and a mild alkali. The water replaces the size on the outer
surface of the fiber, and absorbs within the fiber to remove any fabric residue.
Assessment of size removal:
A drop of iodine solution placed on a test specimen resulting in a characteristic blue color is the
universal test for identifying starch. It can be used as a qualitatively test to show whether all the
starch was removed. Absence of the blue color signifiesthat all the starch has been removed. The
intensity of the color is some what related to how much is left. Usually, if the color is faintly
perceptible, the remaining starch will come out in the scouring and bleaching steps that follow.

précédant sommaire suivant

2.6 Pretreatment
Pretreatment processes should ensure:

· the removal of foreign materials from the fibres in order to improve their uniformity,
hydrophilic characteristics and affinity for dyestuffs and finishing treatments

· the improvement of the ability to absorb dyes uniformly (which is the case in mercerising)

· the relaxation of tensions in synthetic fibres (without this relaxation of tension, unevenness and
dimension instabilities can occur).

The position of pretreatment within the production scheme is closely related to the position of
dyeing in the sequence. The point is that pretreatment comes immediately before dyeing (and
printing).

Pretreatment processes and techniques depend:

· on the kind of fibre to be treated: for raw goods made of natural fibres such as cotton, wool,
flax and silk the technical task is more difficult than for those made of synthetic and artificial
fibres. Natural fibres in fact are accompanied by a higher amount of substances that can interfere
with later processing. Man-made fibres, in turn, usually contain only preparation agents, water-
soluble synthetic size and soil

· on the form of the fibre (flock, yarn, woven or knitted fabrics)

· on the amount of material to be treated (for example, continuous methods are more efficient,
but are economically viable only for large production capacities).

Pretreatment operations are often carried out in the same type of equipment used for dyeing (in
batch processing, in particular, the material is most often pretreated in the same machine in
which it is subsequently dyed). For ease of reading of this part of the document, machines that
are not specific to a given treatment are described in a separate annex (see Section 10).

2.6.1 Pretreatment of cotton & cellulose fibres

[Link] Principal manufacturing processes

Cotton pretreatment includes various wet operations, namely:

· singeing

· desizing

· scouring

· mercerising (and caustification)

· bleaching.

Some of these treatments are obligatory steps only for certain make-ups (e.g. desizing is carried
out only on woven fabric).

Moreover some of these treatments are often combined together in one single step in order to
respond to the need to reduce production time and space as much as possible. Nevertheless, for
practical reasons they will be described as separate treatments, leaving the discussion about
possible process sequences for specific make-ups to the following sections.

Singeing

Singeing can be carried out both on yarns and woven fabrics, but it is more common on fabrics,
especially on cotton, cotton/PES and cotton /PA substrates.

Protruding fibre ends at the fabric surface disturb the surface appearance and produce an effect
known as "frosting" when dyed. It is therefore necessary to remove the surface fibres by passing
the fabric through a gas flame. The fabric is passed over a row of gas flames and then
immediately into a quench bath to extinguish the sparks and cool the fabric. The quench bath
often contains a desizing solution, in which case the final step in singeing becomes a combined
singeing and desizing operation.

Before singeing, the fabric is combed under aspiration to eliminate remaining dust and fibres.

Singeing has no effect on the effluents because only cooling water is necessary. During singeing
relatively strong odours and emissions of dust and organic compounds are observed [209,
Germany, 2001]. Odorous substances can be destroyed using catalytic oxidation techniques (see
Section 4.10.9).

Desizing

Desizing is used for removing from woven fabric sizing compounds previously applied to warp
(see Section [Link]) and is usually the first wet finishing operation performed on woven fabric.

Desizing techniques are different depending on the kind of sizing agent to be removed.

Currently applied techniques can be categorised as follows:

1. techniques for the removal of starch-based sizing agents (water-insoluble sizes)

2. techniques for the removal of water-soluble sizes

3. techniques for the removal of water soluble and insoluble sizes.

1. Techniques for the removal of starch-based sizes

Starch-based sizes are difficult to remove and require either catalytic action of an enzyme
(catalytic degradation) or other chemical treatment in order to be converted into a washable
form. This chemical degradation is mainly achieved by either enzymatic or oxidative desizing.

Enzymatic desizing is the most widely used method for the removal of starch, amylases being
particularly suitable. The advantage in the use of enzymes is that starches are decomposed
without damaging cellulose fibre.

In order to reduce the number of steps in the pretreatment process, it is common practice to
combine desizing with cold bleaching in a single step. In this case the process is also called
"oxidative desizing". The fabric is impregnated in a bath containing hydrogen peroxide and
caustic soda, together with hydrogen peroxide stabilisers and complexing agents. Persulphate is
also usually added to the solution.

Due to the action of NaOH, this treatment, beside a desizing/bleaching effect, also serves as a
pre-scouring treatment. Furthermore, oxidative desizing is particularly useful when the textile
contains enzyme poisons (fungicides) or when sizes are present that are difficult to degrade.
However, because starch scarcely differs from cellulose in the cross-linking of the cellulose
rings, chemical oxidation, if not well controlled, can damage the fibre.

Desizing is usually carried out in pad-batch, but discontinuous (e.g. jigger) and continuous (pad-
steam) processes can also be applied. In the case of enzymatic desizing, pad-steam is applied
only for big lots and with enzymes that are stable under steaming conditions. After the reaction
time, the fabric is thoroughly washed in hot water (95 °C).

2. Techniques for the removal of water soluble sizes

The removal of water-soluble sizes such as PVA, CMC and polyacrylates, theoretically only
requires washing with hot water and sodium carbonate. However, the washing efficiency can be
increased by:

· adding suitable auxiliaries (wetting agents) to the desizing liquor (with some restrictions in case
of size recovery)

· allowing adequate time for immersion in the desizing liquor (this ensures maximum liquor
pick-up and adequate time for the size to swell)

· washing thoroughly with hot water in order to remove the solubilised size.

In this case the process is carried out in normal washing machines. Continuous washers are often
used, but sometimes the treatment time may be too short to allow complete desizing. Pad-batch
and pad-steam or discontinuous processes for prolonging the residence time are therefore also in
use.

3. Techniques for the removal of water soluble and insoluble sizes

The «oxidative desizing» technique mentioned above is applicable not only for water insoluble
sizing agents, but also for water soluble ones. This technique is particularly useful for textile
finishers dealing with many different types of fabrics and therefore sizing agents (see also
Section 4.5.2).

Mercerising

Mercerising is carried out in order to improve tensile strength, dimensional stability and lustre of
cotton. Moreover an improvement in dye uptake is obtained (a reduction of 30 - 50 % of dyestuff
consumption can be achieved thanks to the increased level of exhaustion).

Mercerising can be carried out on yarn in hanks, woven and knitted fabric through one of the
following different treatments:
· mercerising with tension

· caustification (without tension)

· ammonia mercerising.

Mercerising with tension

Caustic soda mercerising is the most commonly applied mercerising technique (it is not applied
to flax). Cotton is treated under tension in a solution of concentrated caustic soda
(270 - 300g NaOH/l, which means also 170 - 350 g NaOH/kg) for approximately
40 - 50 seconds.

During mercerising the temperature is adjusted at low values (5 - 18 °C) when the lustre is the
priority and at slightly higher levels when the improvement of the other characteristics is
preferred. Because the reaction between caustic soda and cellulose is exothermic, cooling
systems are applied to keep down the temperature of the bath.

Beside the conventional cold treatment, a hot mercerising process is also now increasingly
applied (for hanks and fabric). The material is soaked in a solution of caustic soda close to
boiling point. After hot stretching, the fabric is cooled down to ambient temperature and washed
under tension.

In order to ensure a homogeneous penetration of the liquor, especially when operating at ambient
temperature, wetting agents are employed. Sulphonates mixed with non-ionic surfactants and
phosphoric esters are the most commonly used.

Caustification

In the caustification process, the material is treated at 20 - 30 °C with caustic soda at lower
concentration (145 - 190 g/l) without applying tension. The material is allowed to shrink, thus
improving the dye absorption.

Ammonia mercerising

Cotton yarn and fabric can be treated with anhydrous liquid ammonia as an alternative to caustic
soda. Effects similar to mercerising are obtained, although the lustre grade is inferior to caustic
soda mercerising. Traces of ammonia have to be removed, preferably with dry heat treatment
followed by steaming.

This method is not widely used. Only a few plants are reported to use ammonia mercerising in
Europe.

Two examples of mercerising machines respectively for woven fabric ( Figure 2.11) and for
knitted fabric in tubular form ( Figure 2.12) are reported below.
Figure 2.11: Example of Mercerising equipment for woven fabric

[69, Corbani, 1994]

Figure 2.12: Example of Mercerising equipment for knitted fabric in tubular form

[318, Sperotto Rimar, 2002]

Scouring

Scouring (also known as boiling-off or kier boiling) is aimed at the extraction of impurities
present on the raw fibre or picked up at a later stage such as:

· pectins

· fat and waxes

· proteins
· inorganic substances, such as alkali metal salts, calcium and magnesium phosphates,
aluminium and iron oxides

· sizes (when scouring is carried out on woven fabric before desizing)

· residual sizes and sizing degradation products (when scouring is carried out on woven fabric
after desizing).

Scouring can be carried out as a separate step of the process or in combination with other
treatments (usually bleaching or desizing) on all kind of substrates: woven fabric (sized or
desized), knitted fabric and yarn.

For yarn and knitted fabric, scouring is usually a batch process which is carried out in the same
equipment that will subsequently be used for dyeing (mainly autoclaves or hank dyeing
machines for yarn and overflows, jets, etc. for knitted fabric). Woven fabric is scoured in
continuous mode using the pad-steam process.

The action of scouring is performed by the alkali (sodium hydroxide or sodium carbonate)
together with auxiliaries that include:

· non-ionic (alcohol ethoxylates, alkyl phenol ethoxylates) and anionic (alkyl sulphonates,
phosphates, carboxylates) surfactants

· NTA, EDTA, DTPA, gluconic acid, phosphonic acids as complexing agents, which are used to
remove metal ions (and, in particular, iron oxides, which catalyse the degradation reaction of
cellulose when bleaching with hydrogen peroxide)

· polyacrylates and phosphonates as special surfactant-free dispersing agents

· sulphite and hydrosulphite as reducing agents (to avoid the risk of formation of oxycellulose
when bleaching with hydrogen peroxide).

Bleaching

After scouring, cotton becomes more hydrophilic. However, the original colour stays unchanged
due to coloured matter that cannot be completely removed by washing and alkaline extraction.

When the material has to be dyed in dark colours it can be directly dyed without need of
bleaching. On the contrary, bleaching is an obligatory step when the fibre has to be dyed in
pastel colours or when it will need to be subsequently printed. In some cases, even with dark
colours a pre-bleaching step may be needed, but this is not a full bleaching treatment.

Bleaching can be performed on all kinds of make-ups (yarn, woven and knitted fabric).

The most frequently used for cellulosic fibres are oxidative bleaches, namely:
· hydrogen peroxide (H2O2)

· sodium hypochlorite (NaClO)

· sodium chlorite (NaClO2).

Apart from these, peracetic acid is also applicable [7, UBA, 1994]. Also optical brightening
agents are commonly used to obtain a whitening effect.

Bleaching with hydrogen peroxide

Bleaching can be carried out as a single treatment or in combination with other treatments (e.g.
bleaching/scouring or bleaching/scouring/desizing can be carried out as single operations).

The textile is treated in a solution containing hydrogen peroxide, caustic soda and hydrogen
peroxide stabilisers at pH 10.5 - 12 (the optimal pH for scavenging of the OH* radical is 11.2, as
described in Section 4.5.6). Recent investigations ([210, L. Bettens, 1995]) have shown that the
bleaching agent of peroxide is not the anion HOO-, but the dioxide radical anion OO*- (also
known as superoxide). In competition with the formation of the bleaching agent, the OH* radical
is formed, which is responsible for attacking and depolymerising the cellulose fibre. The
formation of the OH* radical is catalysed by metals such as iron, manganese and copper. The
prevention of catalytic damage as a consequence of uncontrolled formation of OH* is mostly
taken care of by using complex formers that inactivate the catalyst (stabilisers). Sodium silicate
together with Mg salts (MgCl2 or MgSO4) and sequestering/complexing agents (EDTA, DTPA,
NTA, gluconates, phosphonates and polyacrylates) are commonly used as stabilisers (see also
Section 8.5 for more information about stabilisers and Sections 4.3.4 and 4.5.6 for alternative
techniques).

Other auxiliaries used in hydrogen peroxide bleaching are surfactants with emulsifying,
dispersing and wetting properties. Employed surfactants are usually mixtures of anionic
compounds (alkyl sulphonates and alkyl aryl sulphonates) with non-ionic compounds such as
alkylphenol ethoxylates or the biologically degradable fatty alcohol ethoxylates [186, Ullmann's,
2000].

Operating temperatures can vary over a wide range from ambient to high temperature.
Nonetheless, a good bleaching action occurs when operating at around 60 - 90 °C.

Bleaching with hydrogen peroxide in neutral conditions (pH range of 6.5 - 8) is also possible in
some cases (e.g. when treating cotton in blends with alkali-sensitive fibres such as wool). At
these pH conditions activators are required to give bleaching activity. Note that below pH 6.5
H2O2 decomposes into H2O and O2 by HOO*- / O2* disproportionation. Under these conditions
hydrogen peroxide is wasted (production of inactive O2 gas).

A wide range of bleaching processes can be used, including cold pad-batch, bleaching under
steaming conditions and bleaching processes in long bath.
Because the bleaching agent of peroxide is anionic in nature (hydrophilic behaviour), it is not
possible with this bleaching method to destroy selectively the coloured hydrophobic material
present on natural fibres without attacking the polymer itself.

Bleaching with sodium hypochlorite

The high reactivity of this bleaching agent imposes softer operative conditions than hydrogen
peroxide (pH 9 - 11 and temperatures not above 30 °C). Otherwise there is a risk of damage to
the cellulose fibre.

The bleaching stage is followed by an anti-chlorine treatment in order to eliminate completely

the hypochlorite and decompose the chloroamines generated during bleaching.

Bleaching with sodium hypochlorite can be carried out in batch (e.g. overflow, jet, jigger, winch
beck), semi-continuous (pad-batch) or continuous mode. A two-stage process is also in use in
which hypochlorite and hydrogen peroxide are used.

The use of hypochlorite as bleaching agent is in decline for ecological reasons. It is still applied
for yarn and knitted fabric when a high degree of whiteness is required, for articles that remain
white (e.g. linen), or require a white background or in processes where the ground-dye is
discharged with a bleach treatment (see also Section 4.5.5 for alternative techniques).

Bleaching with sodium chlorite/ chlorate

Chlorite/chlorate bleaching, although in decline, is still applied for synthetic fibres, cotton, flax
and other cellulosic fibres, often in combination with hydrogen peroxide.

The bleaching agent is the chlorine dioxide gas (ClO2), which follows a completely different
working mechanism compared to hydrogen peroxide. Whereas the superoxide radical ion in
hydrogen peroxide is hydrophilic and therefore works preferentially in the hydrophilic region of
the fibre (attack of the fibre polymer), ClO2 absorbs preferentially on the hydrophobic associated
material, such as the woody part of bast fibres. For this reason it is an excellent bleaching agent
(ensuring a high degree of whiteness and no risk of damage of the fibre) especially for synthetic
fibres and for bast fibres such as flax where, compared to cotton, there is a higher percentage of
hydrophobic impurities.

Because chlorine dioxide is unstable as a gas and can only be stored as a solution of
approximately 1 % in water, it must be generated on-site as an aqueous solution. There are two
ClO2 precursor chemicals in present general industrial use, namely sodium chlorite and sodium
chlorate. Although sodium chlorate is considerably less expensive than sodium chlorite, it is
more difficult and expensive to convert to ClO2, which explains why it is less commonly used.

Both sodium chlorite and sodium chlorate are used in strong acid conditions (pH 3.5 - 4 by
formic or acetic acid). Chlorine dioxide solutions have a great corrosive action on construction
materials including stainless steel. Sodium nitrate is used as a corrosion inhibitor to protect the
stainless steel parts of equipment. It is also necessary to select detergent/wetting agents that can
resist acid conditions. On the other hand, sequestering agents are not necessary because the
oxalic acid used for acidification also serves for sequestering metals. The order of introduction of
the different auxiliaries has to be controlled to avoid direct contact between the concentrated
sodium chlorite/ chlorate solution and acids.

The textile material is bleached by padding or in long bath processes. The temperature is
normally kept at 95 °C, but cold procedures have also been developed to diminish toxicity and
corrosion problems, using formaldehyde as an activator for sodium chlorite.

The advantages of chlorine dioxide bleaching are the high degree of whiteness and the fact that
there is no risk of damage to the fibre. The main disadvantages are the high stresses to which the
equipment is subjected and the chlorine residues that may be left on the fibre, depending on the
way chlorite (or chlorate) is produced and activated. Recent technologies using hydrogen
peroxide as the reducing agent of sodium chlorate are now available to produce ClO2 without
generation of AOX (see also Section 4.5.5).

Bleaching with peracetic acid

Peracetic acid is produced from acetic acid and hydrogen peroxide. It can be purchased as ready-
made product or produced in-situ. Its optimal bleaching action is reached only in a very narrow
pH range between 7 and 8. Below pH 7 the degree of whiteness decreases sharply and above pH
9 depolymerisation of the fibre with consequent damage of the fibre occurs.

Peracetic acid is sometimes applied for synthetic fibres (e.g. polyamide) where hydrogen
peroxide cannot be used.

[Link] Environmental issues

The main environmental issues associated with cotton pretreatment arise from emissions to
water.

The characteristics of the emissions vary according to a number of factors: the make-up, the
sequence adopted, the fact that some treatments are often combined in a single step, etc.

The most relevant issues are highlighted below for the various operations involved in
pretreatment.

Desizing and scouring

In a typical mill processing cotton or cotton-blend woven fabric, desizing represents the main
emission source in the overall process. As already stated in Section [Link], the washing water
from desizing may contain up to 70 % of the total COD load in the final effluent, especially in
the case of native sizing agents. Neither enzymatic nor oxidative desizing allows size recovery,
while for some synthetic sizing agents size recovery is technically feasible, but difficult to apply
for commission companies (see also Section 4.5.1).
Compared to woven cotton fabric, the removal of impurities from yarn and knitted fabric is less
significant in terms of pollution load. Nevertheless, consideration must be given to the COD load
associated with the removal of knitting oils (for knitted fabric), spinning oils and preparation
agents (when cotton is in blend with synthetic fibres) and the biodegradability of these
compounds. Substances such as synthetic ester oils are readily emulsified or soluble in water and
easily biodegraded. More problems are posed by the presence of substances that are difficult to
emulsify and poorly biodegradable such as silicone oils, which are found in elastane blends with
cotton or polyamide.

Mercerising

Mercerising is responsible for a large amount of strong alkali that is discharged in waste water
and needs to be neutralised. The corresponding salt is formed after neutralisation. In this respect,
the cold process involves higher emission loads than the hot one. In order to allow the required
retention time and make possible the cooling of the bath in continuous mode, a portion of the
bath needs to be taken out and cooled down in continuous mode. This means that higher volumes
of bath are necessary in cold mercerising, which result also in higher emissions if the caustic
soda is not recovered. Mercerising baths are usually recovered and re-used. When this is not
possible, they are used as alkali in other preparation treatments (caustic soda recovery is
discussed in Section 4.5.7).

Bleaching with hydrogen peroxide

The decomposition of hydrogen peroxide, which takes place during the bleaching reaction, forms
only water and oxygen. However, environmental concerns associated with the use of stabilisers
have to be taken into account (see Section 8.5). These products may contain complexing agents
such as EDTA and DTPA with poor bio-eliminability, which may pass undegraded through the
waste water treatment systems. Their ability to form very stable complexes with metal makes the
problem even more serious because they can mobilise heavy metals present in the effluent and
release them in the receiving water (see also Section 4.3.4 and 4.5.6 for alternative techniques).

It has been reported ([77, EURATEX, 2000]) that, depending on concentration, pH, time and
temperature, effluents containing inorganic chlorides (e.g. NaCl from dyeing and printing, MgCl 2
from finishing) can be oxidised to their chlorites/hypochlorites when they are mixed with
hydrogen peroxide bleach waste water. In this way AOX may be found in waste water even if
bleaching is carried out without chlorine-based bleaching agents. However, experimental
measurements have shown that this does not play an important role, if any [7, UBA, 1994].

Bleaching with sodium hypochlorite

For ecological reasons the use of sodium hypochlorite is now limited in Europe to just a few
particular cases, connected with knitted fabric and, in some cases, bleaching of yarn when a high
degree of whiteness is required. Bleaching with sodium hypochlorite leads, in fact, to secondary
reactions that form organic halogen compounds, commonly quantified as AOX.
Trichloromethane (which is suspected of being carcinogenic) accounts for the bulk of the
compounds formed, but other chlorinating subsidiary reactions might occur, besides haloform
reaction (see also Section 4.5.5).

When bleaching with hypochlorite, air emissions of chlorine may also occur (although only
under strong acid conditions [281, Belgium, 2002]).

According to the Institute of Applied Environmental Research (Stockholm University), in

1991 - 1992 dioxins were found in sludge from a textile plant that bleached with sodium
hypochlorite. Further investigations showed that pentachlorophenol was present in the
hypochlorite [316, Sweden, 2001].

Bleaching with sodium chlorite

Sodium chlorite bleaching may also be responsible for AOX generation in the waste water.
However, compared to sodium hypochlorite, the amount of AOX formed during chlorite
bleaching is much lower (on average only 10 % to a maximum of 20 % of the amount of AOX
generated by hypochlorite) and it is not correlated with sodium chlorite concentration or with
temperature [7, UBA, 1994]. Recent investigations have shown that the formation of AOX is not
originated by the sodium chlorite itself, but rather by the chlorine or hypochlorite that are present
as impurities or are used as activating agent. Recent technologies (using hydrogen peroxide as
the reducing agent of sodium chlorate) are now available to produce ClO2 without generation of
AOX (see also Section 4.5.5).

As already mentioned earlier, handling and storage of sodium chlorite need particular attention
because of toxicity and corrosion risks. Mixtures of sodium chlorite with combustible substances
or reducing agents can constitute an explosion hazard, especially when they are subject to heat,
friction or impact. Sodium chlorite forms chlorine dioxide when put in contact with acids.
Moreover, sodium chlorite decomposition produces oxygen, which supports combustion.

2.6.2 Wool preparation before colouring

Typical preparation wet treatments applied on wool fibre before dyeing are:

· carbonising

· washing (scouring)

· fulling

· bleaching.

Other possible treatments are those that go under the definition of anti-felt and stabilisation
treatments. Although they are often carried out before dyeing, they are not obligatory preparation
steps. For this reason they have been described under finishing operations (Section [Link]).
[Link] Principal manufacturing processes

Carbonising

Sometimes scoured wool contains vegetable impurities that cannot be completely removed
through mechanical operations. Sulphuric acid is the chemical substance used for destroying
these vegetable particles and the process is called carbonising.

Carbonising can be carried out on floc/loose fibre or on fabric (this operation is not applied in the
carpet sector).

Loose fibre carbonising is performed only on fibres that are later used to produce fine fabric for
garments (worsted fabrics) and usually takes place at the scouring mill.

In typical equipment for carbonisation of loose fibre, the still damp scoured wool is soaked in a
solution containing 6 - 9 % of mineral acid (generally sulphuric acid). Excess acid and water are
removed by pressing or by centrifugation until on average 5 - 7.5 % of sulphuric acid and
50 - 65 % of water remain. The fibres are then dried at 65 - 90 °C to concentrate the acid and
baked at 105 - 130 °C (carbonising).

As soon as the wool is dried, it is fed into a machine, which consists of two counter-rotating
rolls. These rolls crush the carbonised particles into very small fragments, which are then easily
removed. The addition of small quantities of detergent to the sulphuric acid improves the yield
and reduces the attack on the wool. In order to prevent the fibre from being gradually degraded,
the pH is finally set to 6 by neutralisation with sodium acetate or ammonia.

Sulphuric acid can be replaced by gaseous HCl or by aluminium chloride. The latter releases HCl
when it is heated: this method is useful for the carbonisation of wool/synthetic fibres mixtures
such as wool/PES, that are too sensitive to sulphuric acid.

After carbonising, the fibre can be carded and then spun before being dyed or it can be dyed
directly in floc form.

Fabric carbonising is typical of woollen fabrics. The operation can be carried out by either the
traditional or the more modern "Carbosol" system.

The conventional procedure is substantially similar to that used for loose fibre. The fabric can be
previously soaked in a water or solvent bath and squeezed, but this step is optional. Then it is
impregnated in a concentrated sulphuric acid solution (acidification) and squeezed (hydro-
extraction) before passing through the carbonising chamber. The carbonised particles are then
removed by mechanical action and subsequent washing. In modern carbonising plants all these
steps are carried out in continuous mode.

The "Carbosol" process, licensed by SPEROTTO RIMAR, uses an organic solvent instead of
water. The equipment consists of three units. In the first one the fabric is impregnated and
scoured with perchloroethylene, in the second the material is soaked in the sulphuric acid
solution and in the third, carbonising and solvent evaporation take place. At this stage the
perchloroethylene is recovered by distillation in a closed loop.

The «Carbosol» system is reported to have several technical advantages over the traditional
process. The level of acidity of the fabric after carbonising is much lower and the risk of damage
to the wool fibre is reduced. Thanks to full recovery of the organic solvent, the process can also
be considered more efficient from the environmental point of view.

Figure 2.13: Representation of a conventional carbonising installation

[71, Bozzetto, 1997]

Figure 2.14: "Carbosol" system

[71, Bozzetto, 1997]

Scouring
Both yarn and fabric contain, besides accidental impurities, a certain amount of spinning oils and
in some cases also sizing agents such as CMC and PVA. All these substances are usually
removed before dyeing in order to make the fibre more hydrophilic and allow the penetration of
the fibre by dyestuffs. However, this operation is not always necessary. In some cases, if the
preparation agents are applied in low amounts and they do not interfere with the dyeing process,
a separate scouring/ washing step can be omitted.

As pointed out in Section 2.4.1, the percentage of spinning oils on woollen wool is quite relevant
and it is always above 5 %, while on worsted wool it never reaches 2 %.

Typical substances that have to be removed by scouring can be classified as:

· soluble in water

· insoluble in water, but emulsifiable thanks to the action of surfactants

· insoluble in water and non-emulsifiable (or difficult to emulsify) with surfactants. These
substances can be removed only by using organic solvents (in general, halogenated solvents like
perchloroethylene).

As a result the material can be washed (scoured):

· with water or

· with solvent (dry cleaning)

Water washing is carried out in neutral or weakly alkaline conditions (by sodium carbonate or
bicarbonate) in the presence of detergents. Commonly used detergents are mixtures of anionic
and non-ionic surfactants such as alkyl sulphates, fatty alcohols and alkylphenol ethoxylates. In
wool carpet yarn production the scouring process can include simultaneous chemical setting of
yarn twist with reductive agents (sodium metabisulphite) and/or application of insect-resist
agents (see also Section [Link]).

Water scouring is normally a batch operation which is carried out in the equipment in which the
textile material will be subsequently dyed. This means that an autoclave is the commonly used
equipment for yarn, while jets and overflows are the machines typically applied for fabric. In this
respect, the carpet sector is an exception. Wool yarn for carpet is scoured on continuous or semi-
continuous basis in tape scouring machines (hanks) or in package-to-package scouring machines
(package yarn), where the yarn is passed through a series of interconnected bowls (see Section
[Link].2).

Dry cleaning is less common and is applied when the fabric is heavily soiled and stained with
oils from the weaving or knitting process. The most widely used solvent is perchloroethylene. In
some cases water and surfactants are added to the solvent to provide a softening effect.
Solvent washing can be carried out either in discontinuous mode in a tumbler (generally for
knitted fabric) or in continuous mode in open-width (for woven and knitted fabric). Impurities
are carried away by the solvent, which is continuously purified and recycled in a closed loop (see
also Section 2.12.2).

Fulling

This treatment takes advantage of the felting tendency typical of wool fibre when it is submitted
to friction under hot humid conditions and is a typical pretreatment for woollen fabric.

It is usually carried out after carbonising, but in some cases (e.g. heavy woollen fabrics) it can be
done directly on raw fabric. The material is kept in circulation in a bath containing fulling
auxiliaries. Both acids (pH <4.5) and alkali (pH >8) speed up the fulling process. Fulling
auxiliaries available on the market, however, also produce excellent results under neutral
conditions. As a result, fulling either in acid or alkaline conditions is becoming less common.
After fulling, the fabric is washed.

Machines specially designed for this process are still in use. However, today they have been
largely replaced by multifunctional machines, where both fulling and washing can be carried out
by simply adjusting the set-up of the equipment.

Bleaching

Wool is bleached with hydrogen peroxide (sodium hypochlorite may discolour and damage the
wool). An additional reductive bleaching is, however, indispensable for achieving high levels of
whiteness (full bleach). A typical reductive bleaching agent is sodium dithionite (hydrosulfite),
which is often used in combination with optical brightners to enhance its effect.

In the oxidative bleaching step, hydrogen peroxide is applied in the presence of alkali and
stabilisers, which slow down the decomposition of the hydrogen peroxide (see also Section 8.5).

When wool has been previously submitted to an anti-felt treatment it is preferable to use
hydrogen peroxide in weakly acid conditions.

[Link] Environmental issues

Wool pretreatment gives rise mainly to water emissions, although there are also specific
operations (e.g. carbonising with the «Carbosol» system and dry cleaning) where halogenated
(mainly perchloroethylene) solvents are employed. The use of halogenated organic solvents
solvents can produce not only emissions to air, but also contamination of soil and groundwater if
their handling and storage is not done using the necessary precautions. Preventive and end-of-
pipe measures include closed-loop equipment and in-loop destruction of the pollutants by means
of advanced oxidation processes (e.g. Fenton reaction). See Sections 4.4.4, 4.9.3 and 4.10.7 for
more detailed information. The process also involves the generation of exhausted active carbon
from the solvent recovery system. This solid waste has to be handled separately from other waste
material and disposed of as hazardous waste or sent to specialised companies for regeneration.
Due to the predominantly batch nature of wool pretreatment operations for all types of make-ups,
the resulting emissions will be discontinuous and with concentration levels largely influenced by
the liquor ratios used. An exception is represented by carpet yarn which can be scoured/ bleached
and mothproofed on tape or "package to package" scouring machines (see Section [Link].2)
giving rise to continuous flows.

The pollutants that can be found in the waste water, originate in part from the impurities that are
already present on the fibre when it enters the process sequence and in part from the chemicals
and auxiliaries used in the process.

Pollution originating from impurities present on the raw material

Residues of pesticides used to prevent the sheep becoming infested with external parasites can
still be found on scoured wool in amounts which depend on the efficiency of the scouring
process. These are mainly organophosphates (OPs) and synthetic pyrethroid (SPs) insecticides
and insect growth regulators (IGRs), but detectable residues of organochlorine pesticides (OCs)
can be observed. They partition between the fibre and the water according to their stronger or
weaker lipophylic character and, as a consequence, traces of these compounds are released in the
waste water. More information about ectoparasiticides can be found in Sections [Link] and
[Link]. The partition factors of the different classes of pesticides are discussed in more detail for
the carpet sector in Sections [Link] and [Link].

Note that because of their steam volatility some pesticides (OPs) end up in the air emissions from
open machines. This must be taken into account in input/output balances.

Spinning lubricants (see 8.2.3), knitting oils (see 8.2.5) and other preparation agents also
represent an important issue in wool pretreatment. These substances are removed during the
scouring process, contributing to the COD load and aquatic toxicity in the final effluent. The
main concerns are about:

· poorly refined mineral oils (content of aromatic hydrocarbons)

· APEO (non-biodegradable and giving rise to toxic metabolites)

· silicones (non-biodegradable and difficult to remove without scouring assistants)

· biocides (toxic to aquatic life).

The dry spinning route in the carpet sector, described in Section [Link], represents one
exception because in this case spinning lubricants do not reach the water effluent.

Pollution originating from chemicals and auxiliaries used in the process

Considerable amounts of surfactants are used in pretreatment as detergents, wetting agents, etc.
Surfactants with good biodegradability with acceptable performance are now available (see
Section 4.3.3). Nevertheless, the use of alkylphenol ethoxylates is still common in some
companies due to their low cost. Alkylphenol ethoxylates (APEOs) and in particular nonylphenol
ethoxylates (NPEs) are under pressure due to the reported negative effects of their metabolites on
the reproduction system of aquatic species. The environmental issues arising from surfactants in
common use are discussed in Section 8.1.

Other pollutants of concern that may be found in water effluent from pretreatment activities are:

· reducing agents from bleaching treatments and chemical setting of carpet wool yarn (sodium
metabisulphite): they contribute to oxygen demand in the waste water

· poorly bio-eliminable complexing agents (e.g. EDTA, DTPA, phosphonates) from hydrogen
peroxide stabilisers, etc.

· AOX from sodium hypochlorite bleaching

· insect-resist agents in wool carpet yarn production.

More details regarding environmental issues associated with the above-mentioned substances are
given elsewhere in this document, in particular in Section [Link] and Section 8.5.

2.6.3 Pretreatment of silk

The following information has been submitted by Italy [206, Italy, 2001]

Scouring

To prepare a silk yarn for dyeing and silk fabrics for dyeing and printing, it is necessary to
partially or completely remove sericin, as well as natural oils and organic impurities. Depending
on the percentage of sericin removed during scouring (sericin is present in raw silk in a ratio
between 20 % to 25 %), the end-product is defined as unscoured (used only for shirts and suits),
`souple' or degummed.

Scouring can be carried out either on the yarn or on the fabric. It is easier to remove sericin more
evenly by performing the operation on the yarn itself. Nevertheless, the operation is generally
carried out on the fabric, in order to exploit the protective action of this «natural size» against
possible damage during weaving.

The scouring treatment can be carried out in a neutral, acid or alkaline solution, depending on the
desired results. At the industrial level, treatment in alkaline conditions is by far the most
common. It is extremely important to control the temperature.

Scouring baths present a high total organic charge; the concentration of nitrogen organic
components in particular is high.

«Unscoured» silk
The process to produce «unscoured» silk consists in removing from raw silk fabrics all residual
substances from previous operations, with a minimal elimination of sericin (1 % - 2 %), so that
the fabric keeps the characteristic stiff-handle. The operation is carried out in a slightly alkaline
soap bath at low temperature.

«Souple» silk

The process is carried out on weft yarns under acid conditions. The loss of weight is
approximately 10 %.

Degummed silk

This treatment is carried out on both yarns and fabrics and ensures a complete elimination of
sericin, as well as substances added in previous operations, without modifying the fibroin.

Hydrolytic degradation of the sericin protein macromolecule can be obtained by simply using
soaps, by using synthetic surfactants or mixtures of soaps and synthetic surfactants, by means of
an enzymatic treatment, or by treating the silk in water at high temperature and under pressure.

In the degumming process with soap, yarn and fabric are plunged into two baths (degumming
baths). Each bath contains green soap at different concentrations. The treatment is followed by
washing with ammonia and rinsing. The process temperature varies between 95 °C and 98 °C.
The soap concentration in the degumming bath varies between 10 g/l and 15 g/l. On average the
entire treatment lasts for 2 hours. It is possible to re-use exhausted baths after appropriate
addition of soap.

Degumming with synthetic detergents implies the partial or total replacement of soap with
synthetic non-ionic surfactants (e.g. ethoxylate fatty alcohol). It is also possible to combine a
degumming treatment with an oxidizing or reducing bleaching and, in some cases, even with
dyeing, thus improving water and energy saving. Generally, alkali and detergent mixtures are
used at temperatures around 95 °C - 98 °C. Such a treatment is suited to continuous processing.

Degumming under pressure at high temperature is a specific treatment essentially used to degum
yarns. It is necessary to prepare an aqueous bath without surfactants and the temperature should
be between 110 °C and 140 °C. A post-treatment washing is required to eliminate substances
used in previous processes.

Weighting

The weighting operation is carried out mostly on yarns to promote recovery of the weight loss
after the removal of the sericin. The treatment consists in the deposition of tin salts or in grafting
polymer chains to the functional groups of the fibroin protein chain.

Weighting is defined as «equal» if the final substrate weight is the same as it was before
degumming, and as «higher» if the weight is higher. Weighted silk is different in touch and in
draping. The most frequently applied procedure is a «mix weighting» process.
Weighing with minerals

The silk yarn undergoes a treatment using tin tetrachloride in baths at different concentrations
(strong or weak baths) in an acid medium. In a strong bath, silk can increase its weight by about
10 % simply by absorbing the salt. The procedure is followed by accurate washing cycles to
eliminate unfixed salt and to hydrolyse the salt present on the fibre. Such operations can be
repeated to further increase the silk weight. To ensure fixation of tin salts, weighting is
completed with a treatment in a sodium phosphate bi-basic solution, followed by a second
treatment in sodium silicate.

Disadvantages of this procedure are the long processing time and the high water and energy
consumption. The high amount of tin in the waste water is an environmentally undesirable effect
of this process.

Weighing with vinyl monomers

Grafting vinyl monomers onto silk represents an alternative to the traditional mineral weighting.
Such a method not only allows the desired weight increase to be achieved, but also improves silk
characteristics and performance. Co-polymerization with vinyl monomers is carried out using
radical activation methods (redox systems, UV, ã rays and so on).

Methacrylamide (MAA) is one of the most frequently applied monomers at the industrial level.
MAA weighting is a simple application. Radical activation is obtained through ammonia or
potassium persulphate. Other radical activators, which consist of redox systems described in the
literature, are not currently applied at the industrial level.

Silk dyeing behaviour can be modified through the weighting treatment. Studies prove how the
dyeing affinity of silk weighted with MAA towards the most widely used dyes changes
according to the percentage of acquired weight. They also show that wet fastness is reduced in
dyeing after weighting.

For the weighting of silk for ties, methacrylamide is the only technique used by industry; at
present no MAA substitute is available on the market.

Mix weighting

To achieve a hybrid of the final characteristics of compounds submitted to mineral or MAA

weighting, a fairly widely used weighting process on the industrial level is mix weighting with
tin/MAA.

2.6.4 Pretreatment of synthetic material

[Link] Principal manufacturing processes

Typical operations before colouring are washing and thermofixing (heat-setting).

Washing is necessary to remove from the yarn the preparation agents that have been applied to
its surface in the previous treatments (usually 2 - 3 %, but can be up to 4 % of the weight of the
fibre). Most preparation agents (about 95 %) are removed at this stage (ethoxylated fatty alcohols
are commonly used as emulsifying agents). Elastomeric fibres (elastan) are an exception because
they contain preparation agents mainly made up of silicone oils in the order of 6 - 7 %. Silicones
are more difficult to remove and partly still remain on the fibre (40 % of the initial add-on) after
washing. To improve their removal it is common practice to use ethoxylated nonylphenols.

When pretreating woven fabric the removal of sizing agents is a crucial step. The extraction of
these substances is achieved thanks to the synergistic action of:

· surfactants (non-ionic or mixtures of non-ionic and anionic): they act as wetting and
emulsifying agents and promote the solubilisation of the size

· complexing agents (e.g. phosphonates): they are used when there is a risk of re-precipitation of
the components of the sizing agents. An increase in hardness level can occur, particularly, in
continuous lines when processing synthetic blends with cellulose fibres (characterised by the
presence of Ca, Fe and Mg salts as natural impurities)

· alkali (caustic soda or sodium carbonate): the alkali is chosen according to the sizing agent
employed (for example for the removal of sizing agents based on polyacrylates ammonium salts
the use of caustic soda is obligatory, while a polyester sizing agent would precipitate in the same
pH conditions).

Thermofixation is also another important operation in synthetic fibres pretreatment. Its position
within the process can be different, depending on the make-up and the fibre. As a result the
following possible sequences are possible:

1. thermofixation - washing - dyeing

2. washing - thermofixation - dyeing

3. washing - dyeing - thermofixation.

If white fabrics are to be produced, bleaching of the fabric may be necessary after
thermofixation.

[Link] Environmental issues

Potentially harmful impurities and additives are already present on synthetic fibres before they
are processed at the finishing mill and they account for a large fraction of the pollution load
coming from pretreatment.

Some of these impurities are produced during the manufacture of the fibre. They are polymer
synthesis by products such as unreacted monomers (for example caprolactame, in the production
of PA 6) low-molecular-weight oligomers, and residual catalysts and they are emitted to air
during thermal treatments.

Other substances are intentionally added to the fibre to improve subsequent processing. These
are the preparation agents used in fibre and yarn manufacturing and the sizing agents.

The average amount of preparation agents applied on man-made fibres (except for elastomeric,
where the load can be much higher) ranges between 2 and 4 % of the weight of the fibre (see also
Section 8.2).

When the textile is washed, about 80 % of these substances are released to the waste water and
the remaining 20 % can be emitted to exhaust air in the subsequent high temperature treatments
(drying and thermofixation). Conversely, when thermofixation is carried out on the grey material
before washing (which is the case when fine woven and knitted fabric are processed), the main
percentage of pollution load is found in the exhaust air.

During high-temperature treatments the lower molecular weight components of the preparation
agents (basically lubricants and surfactants) either decompose -- resulting in smaller, more
volatile molecules -- or they react with each other, forming tar. Volatility and tar are undesirable
effects because they lead to air emissions and damage to the yarn.

However, thanks to considerable technological improvements achieved by the technology in the

field of synthetic fibres, the fibres/filaments leaving the primary spinning process (fibre
production) no longer cause fuming. The remaining problems today are connected with those
cases where, after the fibre/filament production, lubricants such as coning oils are added to the
fibre at a rate of over 2 or even 3 % of the yarn weight [48, VITO, 2001].

The main concerns, as regards waste water, arise from the discharge of poorly or non-
biodegradable substances such as mineral oils, EO/PO adducts, silicone oils, hard surfactants,
etc. Furthermore, biocides, which are normally contained in the aqueous formulations, contribute
to aquatic toxicity of the waste water.

Likewise for air emissions, as for water emissions, the main charging load in waste water again
comes from the preparation agents (coning oils, overspray, etc.) that are applied to the
fibre/filament after the primary spinning stage. These substances (secondary spinning agents) are
applied in significantly higher amounts than primary spinning agents. Moreover, they usually
have low affinity with water and are therefore difficult to remove.

For woven fabric, sizing agents also have to be considered. Sizing agents do not give rise to air
emissions during HT treatments, but they may be responsible for poorly biodegradable
substances and aquatic toxicity.

Information about alternative preparation agents for man-made fibres is given in Section 4.2.1.

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