Bleaching : Ullmann's Encyclopedia of Industrial Chemistry : Wiley InterScience

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Hans Ulrich Süss1 Print this page
1Degussa AG, Hanau-Wolfgang, Germany
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Copyright © 2006 by Wiley-VCH Verlag GmbH & Co. KGaA. All rights
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DOI: 10.1002/14356007.a04_191.pub2 Advanced Product Search
Article Online Posting Date: December 15, 2006 Search All Content
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Abstract
The article contains sections titled:

1. Introduction
2. Bleaching Agents
2.1. Pretreatment
2.2. Oxidizing Agents
2.2.1. Oxygen
2.2.2. Chlorine Dioxide and Sodium Chlorite
2.2.3. Hydrogen Peroxide and Other Peroxo Compounds
2.2.4. Ozone
2.2.5. Chlorine and Hypochlorites
2.3. Reducing Agents
2.3.1. Sodium Dithionite
2.3.2. Sulfur Dioxide
2.3.3. Sulfinic Acid Derivatives
3. Enzymes
4. Bleaching Processes
4.1. Pulp
4.1.1. Chemical Pulp
4.1.2. Mechanical Pulp
4.1.3. Paper Recycling (Deinking)
4.1.4. Environmental Aspects of Pulp Bleaching
4.2. Textile Fibers
4.3. Other Products

Bleaching is the removal of color from various materials. It is predominantly achieved by an oxidative or reductive treatment,
which destroys chromophores. In principle all oxidizing or reducing chemicals can act as bleaching agents, but on an
industrial scale only a few compounds are used in bleaching processes. Chlorine dioxide, hydrogen peroxide, and sodium
dithionite are predominantly applied. The alternative to a chemical reaction is the adsorption of colored impurities on pigment
surfaces, like active carbon or bleaching clays. This method is applied mainly in purification or bleaching of liquids.

A bleaching process removes impurities; thus, in parallel the bleached good is cleaned. The “art of bleaching” is to reach a
desired decrease in color with the least negative impact on quality and properties of the bleached material. Chemicals and
processes are selected on the basis of their ability to achieve brightness and quality targets with a small amount of
byproducts or residuals and low impact on the environment.

Bleaching of fibers for paper production is the most important industrial application. Highest effectiveness is guaranteed by a
combination of several process steps in a bleach plant. Textile fabric bleaching is the second most important application.
Modern bleaching technology aims for the most moderate use of resources, the lowest consumption of water, and best
biodegradability of the compounds dissolved during the bleaching process.

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Bleaching : Ullmann's Encyclopedia of Industrial Chemistry : Wiley InterScience
1. Introduction
A bleaching effect is achieved by a removal of chromophores. This can be achieved by adsorption of the colored compounds
on active surfaces like active carbon or bleaching clays. On an industrial scale this option is used to bleach and purify liquids
like vegetable oil. Bleaching by chemical destruction of chromophores in organic or inorganic compounds is more common.
Industrially, decolorization is often combined with purification or cleaning. Components affecting material quality, handling
properties, or marketability of a product are removed. This is especially important for natural products, most of which contain
impurities. For example, cotton is contaminated with seed-capsule residues, wax, fatty constituents, and inorganic
compounds. Bleaching cotton increases brightness while simultaneously removing impurities. Bleaching also can continue or
supplement an earlier processing step. For example, in continuation of chemical pulping bleaching removes lignin from wood
fibers, thus brightening and further purifying the cellulose.

Very few compounds can be bleached nearly colorless without damage. The “art of bleaching” is to achieve a high degree of
chromophore removal without damaging the bleached good. The aim of bleaching from the outset may also be to generate
simply a more uniform hue, e.g., bleaching wood veneer.

In terms of the amount of material processed and the value of the product, bleaching of fibrous materials for paper and textile
production is most important (Table 1). Detailed information about these processes is available under specific keywords (
Paper and Pulp or Textile Dyeing) and in [1], [2], [3]. Table 2 gives a summary of products bleached on industrial
scale.

Table 1. World production of bleached fiber material (103 t)

Material Year Amount

Bleached chemical pulp 2004 80 000

Bleached mechanical pulp 2004 30 000
Cotton* 2004/2005 25 000
Wool (scoured)* 2003 1 260

*Dying is an important part of textiles manufacturing. A prerequisite of the dying process is a certain level of cleaning
and bleaching in order to achieve uniform color distribution. It can be assumed that the predominant amount of fiber
used for textiles production has been bleached during manufacturing.

Table 2. Important products requiring bleaching

Fibers for paper

Chemical pulp,
Mechanical pulp,
Wastepaper, linters
Fibers for textiles
Natural products: cotton, flax, wool, silk

Synthetics: rayon, polyamide, polyester,

polyacrylonitrile, polyurethane
Others
Vegetable products: fatty acids, resins, wax, starch,
flour, vegetable oils, wood, wood
veneer, peeled rattan
Animal products: fatty acids, hair, bristle, feathers,
horn, sponges, mother-of-pearl
Mineral and
synthetic products: paraffin, petroleum, glues,
plastics, soap, sulfuric acid

Bleaching can be classified into oxidative and reductive bleaching. Oxidative bleaching destroys chromophores irreversibly,
while reductive bleaching can be reversible, for example, by reoxidation by atmospheric oxygen.

Especially in the case of natural products, the chemical constitution of the colored compounds is not known in full detail.
Generally these compounds contain conjugated carbon – carbon double bonds, e.g., polymethine chains, aromatic systems,
or quinoid systems. Oxidative bleaching destroys the double bonds, removes the conjugation, and produces chemical
compounds of lower molecular mass. Effective bleaching frequently is a multistep process. The repetition of acidic oxidation

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Bleaching : Ullmann's Encyclopedia of Industrial Chemistry : Wiley InterScience
and alkaline extraction allows moderate conditions and a low concentration of chemicals to be maintained.

The bleaching effect is measured by the increase in brightness. Remission photometers are used to determine brightness
relative to a standard at several wavelengths. BaSO4 is the most widely used standard. However, there are several similar
methods that may be used to determine brightness [4], [5]. The quality and efficiency of bleaching is also reflected by
brightness stability. Excessive oxidation can generate new chromophores or the potential for later yellowing. Yellowing takes
place if the auxochrome groups in a chromophore can be reoxidized. Light and heat may change the color of bleached
materials. Carbon – carbon bonds are readily cleaved by UV radiation to give radicals. Recombination of these radicals with
oxygen or other parts of the molecule can form new chromophores.

In a bleaching processes the degree of polymerization of the polymers treated must not be affected negatively. A decrease in
molecular mass of the polymers may affect fiber strength and reduce the economic value. Therefore, bleaching should
destroy chromophores but not affect the molecular structure. A wide variety of bleaching methods have evolved because of
the various complications resulting from the differences in the raw materials. An example is bleaching of cotton in comparison
to wool. While strong alkaline conditions can be applied in bleaching the carbohydrate polymer cellulose (cotton), the keratin
(protein) wool fiber is very sensitive towards alkali. Extraction of amino acids would destroy the polymer, so alkaline
bleaching cannot be used.

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2. Bleaching Agents
Detailed descriptions of the production and properties of bleaching chemicals are given under the specific keywords (for
example, Chlorine). The following sections are limited to a description of the applications and the advantages or
disadvantages of the major bleaching agents.

2.1. Pretreatment
The removal of contaminants is part of the preparation for a bleaching process. A typical pretreatment might simply be
washing. Sheared wool can contain up to 50 wt % of sand and fatty material (lanolin). Similarly, compounds consuming or
decomposing the bleaching agent must be eliminated before the actual bleaching process. Washing ahead of bleaching in
the presence of surfactants or chelating compounds is a common procedure. This decreases the demand for bleaching agent
and lowers the potential for negative side reactions during bleaching. In chemical pulp bleaching this can be an important
prerequisite of bleaching.

Acid washing below pH 3 solubilizes metal ions. The presence of reducing agents such as sulfur dioxide to lower the
oxidation state of the metals can improve the effect. Chelating agents like the sodium salts of diethylenetriaminepentaacetic
acid [140-01-2], DTPA, or ethylenediaminetetraacetic acid [64-02-8], EDTA, are used under mildly acidic conditions (pH 5–6)
to accelerate the elimination of metals. This pH range allows the removal of transition metals with conservation of
magnesium and calcium ions, which are of benefit as stabilizers in bleaching. For chemical pulp produced by alkaline
pulping, such a metals-removal stage is necessary if totally chlorine free (TCF) bleaching is to be applied. In conventional or
ECF (elemental chlorine free) bleaching metals are removed during the acidic chlorine dioxide stages. In acid sulfite pulping
they are solubilized during the pulping process and removed in brown stock washing.

During alkaline pulping of hardwood xylan polymer double bonds are generated. These hexenuronic acids consume
electrophilic bleaching chemicals. They are hydrolyzed in a hot acid pretreatment below pH 3 at about 90 °C to yield
furancarboxylic acid [6]. This decreases the demand for bleaching chemicals.

Enzymes like xylanase may be applied as pretreatment. During alkaline pulping xylan dissolves but may precipitate again in
the final steps of the cooking procedure. This can cause difficulties in bleaching. Xylanase removes the precipitate and
facilitates bleaching. Preferred products are enzymes extracted from thermophilic bacteria with high temperature and pH
tolerance.

In bleaching of textiles, treatment with amylase or peroxosulfate may be necessary to remove starch.

2.2. Oxidizing Agents

The ancient Egyptians and Phoenicians practiced oxidative bleaching of textiles in sunlight combined with a mild alkaline
treatment using potassium carbonate leached from wood ashes. In the 1700s bleaching of textile fabrics by an alternating
treatment with potassium carbonate, sunlight on grassy meadows, and sour milk was known as “Dutch bleaching”, because it
reached its greatest perfection around Haarlem, in the Netherlands.

The increase in knowledge about chemistry in the late 1700s yielded a new bleaching agent, hypochlorite. For nearly 150
years the hypochlorites of potassium [7778-66-7] (Eau de Javelle), sodium [7681-52-9] (Eau de Labarraque), and calcium [
7778-54-3] developed into the most important industrial bleaching agents. Chlorine was introduced in chemical pulp
bleaching in the 1930s. Chlorine dioxide and hydrogen peroxide followed a decade later.

Industrial use of oxygen as a bleaching agent for chemical pulp started in the late 1960s. Ozone [10028-15-6] was later
added to chemical pulp bleaching sequences. Other oxidizing compounds used for bleaching are derivatives of hydrogen
peroxide, for example, peracetic acid, sodium perborate, peroxodisulfates (persulfates), and peroxomonosulfates (Caro's
acid). These compounds are applied only under special conditions. This also applies for potassium permanganate [
7722-64-7].

2.2.1. Oxygen ( Oxygen)

The use of oxygen [7782-44-7] as a bleaching agent has increased sharply since the early 1970s. It is used in chemical pulp

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bleaching to continue and intensify the lignin degradation process which normally starts with alkaline pulping. Oxygen
delignification needs alkaline conditions (normally NaOH) for the oxidation process, a rather high temperature (75 – 100 °C),
and an oxygen pressure of 0.3 – 0.5 MPa. Increasing the temperature, the pressure, or the caustic soda concentration
increases the rate of oxidation. Oxygen delignification involves two simultaneous reactions: the desired delignification and
undesired carbohydrate degradation. Therefore practical limits exist for temperature increase and the amount of alkali. The
decrease in the degree of polymerization is inhibited to some extent by magnesium salts.

Although the effect of oxygen on chemical pulp is limited, treatment with oxygen decreases the demand for other bleaching
chemicals by 40 – 50 %. Oxygen delignification allows the combined recovery of the effluents from pulping and the
subsequent delignification step, effectively lowering the total amount of organic material discharged from the bleaching plant.

For magnesium-based pulping processes (magnesium sulfite pulping), the oxygen stage can be operated with magnesium
hydroxide or oxide as the alkali source. Typically, hydrogen peroxide is added simultaneously (at about 90 °C) to increase
the rate of delignification.

2.2.2. Chlorine Dioxide and Sodium Chlorite ( Chlorine Oxides and Chlorine Oxygen Acids)
Chlorine dioxide [10049-04-4] is a very selective bleaching agent. The first industrial use in bleaching chemical pulp was in
1946.

Chlorine dioxide has an unpaired electron; therefore, it is a free radical and has limited stability. It is a gas under standard
conditions and explodes spontaneously at partial pressures above 40 kPa, decomposing into chlorine and oxygen. If heated
or exposed to light, it can explode even at lower concentrations, but with less violence. For this reason, pure chlorine dioxide
cannot be transported and stored. It is generated on site and normally handled as dilute aqueous solution.

The basic reaction for industrial chlorine dioxide generation is the reduction of chlorate [14866-68-3]. Historically, reduction
with sulfur dioxide, the Mathieson process, is important:

Dilute sulfuric acid and sodium sulfate or sodium hydrogen sulfate are the byproducts. Other processes, which produce fewer
byproducts, use hydrochloric acid, methanol, or hydrogen peroxide as the reducing agent. The advantage of hydrochloric
acid is very low costs, but the amount of chlorine present as a byproduct in the chlorine dioxide can be rather high (about
20%). In bleaching this results in increased formation of undesired halogenated products. Nowadays the methanol and
hydrogen peroxide processes are the most important. In these processes very pure chlorine dioxide is generated as a gas,
highly diluted with air or water vapor to avoid explosions. It is absorbed in cold water to give a concentration of 6 – 12 g/L.

For reactions of ClO2 with pulp a pH value between 2 and 5 is normal. Within this pH range chlorine dioxide does not affect
the degree of polymerization of cellulose. Typical reaction temperature for chlorine dioxide is between 50 and 75 °C. In
hardwood pulp bleaching it is favorable to start bleaching at very high temperature (> 90 °C), as this allows the simultaneous
oxidation of lignin and hydrolysis of hexenuronic acids.

In bleaching textiles sodium chlorite [7775-09-9] is used as the source of chlorine dioxide. Hydrochloric acid, formic acid [
64-18-6], or acetic acid [64-19-7] is used to liberate ClO2.

2.2.3. Hydrogen Peroxide and Other Peroxo Compounds ( Hydrogen Peroxide; Peroxo Compounds, Inorganic;
Peroxy Compounds, Organic)
Hydrogen peroxide [7722-84-1] has been used as an industrial bleach since the early 1900s. At first the main use was
bleaching textile fibers. Sodium perborate [7632-04-4], NaBO3 · 4 H2O, prepared from sodium peroxide and borax, was used
in the laundry detergent Persil as a bleach as early as 1907. Even today, perborates and percarbonates are used in large
quantities in laundry detergents. Their mild bleaching effect at elevated temperatures is gentler to fibers and therefore
superior to that of the harsher hypochlorites, which are used as so-called cold bleaches. Because of the lower storage
stability of pure percarbonate, specially coated products are applied.

Aqueous solutions of hydrogen peroxide are available in concentrations up to 90 wt %. Solutions with 35 – 70 wt % are
generally applied in bleaching. The most important application of hydrogen peroxide is bleaching of pulp for paper
production. Mechanical pulp and chemical pulp are bleached with alkaline peroxide solutions. Hydrogen peroxide is also
used for bleaching textile fibers such as cotton, flax, wool, and synthetics.

Commercial processes use slightly to strongly alkaline conditions for hydrogen peroxide bleaching. Usually sodium hydroxide
is the source of alkali. The initial reaction is the nucleophilic addition of hydroperoxide anions to carbonyl groups [7].
Therefore, the bleaching rate is increased by addition of alkali:

However, alkaline conditions also favor side reactions like the disproportion of hydrogen peroxide into oxygen and water:

The bleaching result depends on activation and stabilization. The reaction rate increases with temperature and alkali
concentration. However, side reactions such as the thermal decomposition of hydrogen peroxide into radicals become more

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likely or even dominant at high temperatures, which also lead to yield losses due to solubilization of the material being
bleached. Consequently the normal temperature range for peroxide bleaching is between 60 and 90 °C.

Stabilization of the alkaline bleaching liquor may be required to minimize peroxide decomposition. Hydroxyl radicals,
generated by the decomposition of peroxide, are highly unselective oxidizing agents that produce undesired side reactions.
In chemical pulp bleaching the chelation of transition metals is only required in TCF bleaching. In ECF bleaching hydrogen
peroxide typically is applied only following an acidic stage. This removes transition metals in the washing step. In mechanical
pulp bleaching, detrimental metals are best removed by pretreatment with a chelating agent. Typical chelating agents are the
sodium salts of diethylenetriaminepentaacetic acid (DTPA), ethylenediaminetetraacetic acid (EDTA), or the corresponding
phosphonates, which have similar or even better chelating ability. In addition sodium silicate is applied as a stabilizer which
buffers the bleaching liquor. Similarly, magnesium salts (mostly magnesium sulfate, Epsom salt) are used. The effect of the
stabilizers is to precipitate or absorb detrimental compounds on colloidal silica or magnesium hydroxide.

In the bleaching process hydrogen peroxide cleaves side chains and destroys quinoid structures irreversibly. The oxidation
and destruction of quinones is an important prerequisite for achieving good brightness stability. Peroxide-bleached products
show lower reversion compared to other oxidants.

Peracetic acid [79-21-0], CH3COOOH, is used in small amounts as an activation step prior to alkaline hydrogen peroxide
treatment. Its application allows a higher brightness increase or a lower total consumption of bleaching chemicals. The
reaction with pulp is conducted under mild acidic conditions; it is predominantly a hydroxylation reaction of the residual lignin.
Peracetic acid is produced by mixing acetic acid and hydrogen peroxide. In the presence of a strong acid (e.g., sulfuric acid)
an equilibrium between acetic acid, peracetic acid, hydrogen peroxide, and water is rapidly established. As the other
compounds in the mixture do not contribute to the bleaching reaction of peracetic acid the application of equilibrium peracetic
acid is expensive. An option to overcome this problem is the use of distilled peracetic acid. Vacuum distillation of equilibrium
peracetic acid yields a rather pure peracetic acid solution in water. Distilled peracetic acid with a content of about 35 % in
water should be stored only below 4 °C, because at higher temperature the equilibrium with hydrogen peroxide and acetic
acid is again slowly established. An alternative is on-site mixing, which yields a peracetic acid/peroxide mixture which can be
used for an initial peracetic reaction and a subsequent peroxide bleaching step. This is achieved by adding sufficient alkali
after the acidic stage.

Peracetic acid is generated in situ from hydrogen peroxide and tetraacetylethylendiamine (TAED) [10543-57-4] under weakly
alkaline conditions. This procedure is applied in laundering agents with percarbonate or perborate as peroxide source. It is
also applicable in bleaching of specialties.

Potassium peroxosulfate [37222-66-5], KHSO5, is used for bleaching polyamide and cellulose fibers. However, it is ordinarily
used only to clean wool and to reduce its shrinkage. Sodium peroxodisulfate [7775-27-1], Na2S2O8, and ammonium
peroxodisulfate [7727-54-0], (NH4)2S2O8, are used to desize cotton and sometimes as an additive in hydrogen peroxide
bleaching.

2.2.4. Ozone ( Ozone)

Ozone [10028-15-6] is produced from oxygen by silent electrical discharge. For bleaching pulp, ozone is typically produced
from pure oxygen. This allows a high ozone concentration in the gas (up to 12 wt %) and facilitates the mixing procedure.
Ozone is used at a pH below 4. Temperature in ozonation must be kept below about 50 °C to avoid side reactions with the
cellulose caused by the high oxidation potential. At too high a temperature brightness is less stable and yellowing takes place
easily.

2.2.5. Chlorine and Hypochlorites ( Chlorine)

In the past chlorine [7782-50-5] was widely used in chemical pulp bleaching for lignin oxidation (delignification). In
chlorination substitution and oxidation of the aromatic rings in lignin takes place, producing dicarboxylic acid and chlorinated
lignin fragments [7]. About 10 % of the applied chlorine is found as halogenated compounds in the effluent. Chlorinated
phenols and polyhalogenated dibenzodioxins and dibenzofurans are among these products. Quantitative analysis of these
compounds is performed by an extractive method with activated carbon, and the result is expressed as adsorbable
halogenated organic compounds (AOX) [8]. Some of these compounds are mutagenic [9]. In most regions of the world the
application of chlorine was phased out shortly after identification of these compounds in the effluent.

Today hypochlorite is used mainly as stain remover (“cold bleach” in laundering). Like chlorine, it is no longer applied on a
large scale in chemical pulp bleaching. There application is limited to the use of very small amounts for controlled lowering of
the degree of polymerization of dissolving pulp. The oxidation potential of hypochloric acid [7790-902-3], HOCl, is higher
(+ 1.50 V) than that of chlorine (+ 1.35 V) or hypochlorite [14380-61-1] OCl– (+ 0.94 V). To avoid side reactions (mainly
depolymerization) involving the aggressive hypochloric acid, bleaching is carried out in alkaline solutions to minimize the
concentration of undissociated hypochloric acid. Because the hypochlorite anion is only a weak nucleophile, unable to attack
electron-rich aromatic systems, alkaline conditions cause fewer unfavorable side reactions. Bleaching with hypochlorite
generates halogenated compounds in side reactions. However, in comparison to chlorine AOX formation is significantly
lower. Chloroform is the main byproduct. Sodium hypochlorite [7681-52-9] solutions are commercially available with active
chlorine concentrations of 150 – 160 g/L. Active chlorine is the amount of chlorine set free upon acidification of the
hypochlorite solution.

2.3. Reducing Agents

The most important reducing bleaching agent is sodium dithionite. Sulfur dioxide has been used to bleach wool since ancient
times, but it is of less importance today. Sulfinic acid derivatives are used mainly for the removal of colorants from textile
fabrics.

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2.3.1. Sodium Dithionite ( Sulfites, Thiosulfates, and Dithionites)
Sodium dithionite [7631-94-9], Na2S2O4, is still known as hydrosulfite in North America, although this incorrect initial
description was recognized and corrected as early as 1881. Sodium dithionite is today produced from sodium formate and
sulfur dioxide. Zinc dithionite [13986-17-9], prepared from sulfur dioxide and zinc dust, was formerly more important than the
sodium salt. However, the heavy metal zinc causes environmental problems, and today on-site production of zinc dithionite is
no longer practiced. The same applies for production from sodium amalgam and sulfur dioxide. On-site generation of
dithionite from alkaline sodium borohydride solution, sodium bisulfite, and sulfur dioxide is used by some paper mills.

Sodium dithionite is available as crystalline powder (90 % Na2S2O4) or as a refrigerated 150 g/L solution stabilized with
alkali. Solutions should be kept well below 10 °C because dithionite disproportionates to thiosulfate and bisulfite:

Dithionite destroys chromophores by reducing carbonyl groups to alcohols and quinones to phenols. It is used to bleach
mechanical pulp, wool, silk, bristle, hair, straw, soap, glue, kaolin, and foods such as sugar, molasses, gelatin, and edible
fats.

Dithionite is easily oxidized to sulfite and sulfate by oxygen. The solution decomposes at elevated temperatures to
thiosulfate, sulfite, hydrogen sulfide, or sulfur, the exact products depending mostly on pH. The pH selected for bleaching
with dithionite is a compromise between the most effective bleaching and the lowest loss of dithionite. Normally, a pH of 5 – 6
and temperatures of 50 – 80 °C give the best results. In mechanical pulp bleaching, hydrogen peroxide and dithionite
bleaching are often combined in two sequential steps.

2.3.2. Sulfur Dioxide ( Sulfur Dioxide)

Sulfur dioxide [7446-09-5] is used mostly in the form of sodium hydrogensulfite, NaHSO3. Because of the relatively poor
bleaching effect, SO2 is no longer widely used. It can be applied in mechanical pulp production as a pretreatment to dithionite
bleaching. Another use is the treatment of wool.

2.3.3. Sulfinic Acid Derivatives ( Sulfinic Acids and Derivatives)

The important sulfinic acid derivatives are sodium hydroxymethanesulfinate [149-44-0]

and formamidinesulfinic acid [4189-44-0]

Hydroxymethanesulfinates are prepared by treating dithionites with formaldehyde; they are more stable than the dithionites.
Higher temperatures are needed to produce the full reducing power. These sulfinic acid derivatives are therefore used in
processes that operate above 75 °C, in which dithionite would be decomposed rapidly. They are used for bleaching soap,
glue, gelatin, and fatty acids. However, their main use is in dyeing processes.

Formamidinesulfinic acid is prepared from thiourea and hydrogen peroxide. Therefore, it is sometimes called thiourea
dioxide. It is a poorly water soluble crystalline product. It becomes more soluble under alkaline conditions, and it reaches its
highest reducing power above 80 °C. It is used to increase brightness of textiles and to remove dyes from fabrics (like
hydroxymethanesulfinic acid). Its strong reducing power at high temperature favors application in bleaching of secondary
fibers in the dispersing step. It is very effective in the destruction of colorants used for colored paper. By volume this is the
most important application.

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3. Enzymes
The technical use of enzymes in bleaching is still the exception. The discovery of lignin-degrading enzymes in white rot fungi
(Phanerochaete chrysosporium) [10] seemed to open a new option for industrial-scale delignification and bleaching.
However, the reaction was very slow, not selective enough, and the enzyme required coenzymes which degraded cellulose.
This is a general problem of enzyme application. Enzyme strains must be very pure to avoid negative side reactions by
activity of other enzymes. In addition many industrial processes are operated at elevated temperature or extreme pH. Both
require the use of adapted enzymes. Thermophilic organisms are a preferred source for the selection of an enzyme.

Xylanases are used to eliminate part of the precipitated xylan from unbleached kraft pulps [10]. This treatment lowers the
demand for chlorine dioxide in ECF bleaching by approximately 10 %. It is suggested that lignin on the fibers is partly
covered by precipitated xylan, and that removal of the xylan allows this lignin to be washed off more easily. The overall
moderate effect has made xylanase application a niche option for pulp mills with limited availability of chlorine dioxide.

Laccase is the enzyme that polymerizes the phenylpropane units in plants and produces the lignin polymer. With the aid of a
mediator, laccase can be used for the delignification of pulp [11]. Mediators are easily converted to radical cations by reaction

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with laccase and oxygen. The intermediate product oxidizes the lignin. Theoretically, the mediator, for example, N-
hydroxybenzotriazole [2592-95-2], can be reoxidized several times by the enzyme. However, repeated reaction is the
exception. Consequently, demand for the mediator is high. Currently (in 2006), industrial application is not economical.

Cellulases are used to soften cotton fabric. They are applied in the stone washing of jeans as a substitute for the mechanical
effect of pumice stones. This effect on the surface of the fabric causes a fading of the color, because the colorant is located
only on the fiber surface.

Cellulases have also been recommended for improving the fiber strength of wastepaper pulp. The dissolution of fines and
fibrils increases the average fiber length and increases the strength potential. However, this solubilization lowers yield and
increases the effluent load. Therefore, large-scale application remains unlikely.

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4. Bleaching Processes
The bleaching processes for the substances in Table 2 are described in detail in the articles on the substances. (For
example, Paper and Pulp.) The bleaching processes for pulp and textiles, the most important uses economically, are
briefly summarized here.

4.1. Pulp ( Paper and Pulp)

Fibers used for paper production are predominantly bleached [2]. A distinction can be made between the main types of paper
fibers: chemical pulp and mechanical pulp. Wastepaper typically is a mixture of both types of fibers and contains in addition
fillers such as china clay and calcium carbonate and printing ink.

4.1.1. Chemical Pulp

The most important method for the production of chemical pulp is the alkaline kraft or sulfate process, which is by far the
dominant process worldwide. The acidic sulfite process plays a very minor role with a production share below 5 %. An
oxidative process is required to destroy the residual lignin polymer. Because each bleaching agent has its specific
advantages and disadvantages, generally several chemicals are applied in a sequence of steps. Bleaching is carried out
continuously in towers or reactors. Between the steps, washing is carried out in drum, belt, displacement, press or diffusion
washers. The bleachability of a pulp depends upon the pulping procedure. In general, kraft pulps require more effort and
more bleaching steps to reach very high brightness. Typical market pulp brightness for softwood pulp is > 88 % ISO. The
brightening process requires between four and six stages. Hardwood pulp is available with a brightness of 90 % ISO and
higher. The abbreviations used to describe a bleaching sequence are listed in Table 3.

Table 3. Bleaching stage designations, conditions, and effects

Designation Conditions and effects

O oxygen stage for oxidation of lignin with molecular oxygen under alkaline conditions
at 90 – 100°C.
A acid stage to remove transition metals (at 40 – 60°C) or hexenuronic acid (at > 90°
C) by hydrolysis; the acid typically is sulfuric acid.
Q acidic stage (pH 5 – 6.5) with chelating agents (e.g., EDTA or DTPA) for transition
metals removal.
D chlorine dioxide stage using a solution of ClO2 at pH < 5 in water for lignin oxidation.
E extraction stage using caustic soda for solubilization of oxidized lignin (pH 9.5 – 11).
Eo extraction with addition of oxygen gas for improved lignin removal by oxidation.
Eop extraction reinforced with oxygen and hydrogen peroxide for improved lignin
removal by oxidation and brightening.
P alkaline bleaching stage with hydrogen peroxide, (pH >10 – 11, 60 – 90 °C).
OP pressurized peroxide stage with addition of oxygen, potentially operated above 100 °
C with up to 0.3 MPa pressure.
Z delignification stage with gaseous ozone.
Paa weakly acidic stage (pH 5) with peracetic acid for lignin oxidation and activation for
subsequent P stage.
X enzyme treatment stage with xylanase or other hemicellulases to improve lignin
accessibility by removal of precipitated carbohydrates.
Y reductive treatment with dithionite.
N neutralization.

Bleaching sequences are described by a sequence of these letters, e.g, ODED. In this combination the washing procedure
between the stages is not explicitly mentioned. A combination without intermediate washing can be indicated by the use of
brackets, e.g., (ZD). The way of combining the letters is not standardized. Sometimes in a combination of letters the capital
letter is used to describe the main purpose of the stage; the combination “Eo” stands for an extraction stage with a support of
the extraction by oxygen addition. Sometimes the description EO is used for the same purpose. A glossary of bleaching

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terms is available in [12].

In the past in chemical-pulp bleaching chlorine was used as the main delignification chemical (abbreviated by C). Its
selectivity in lignin oxidation and the low level of side reactions with cellulose made it the preferred delignification compound
for some decades. A serious disadvantage is the generation of a large amount of various halogenated compounds with
limited biodegradability. The detection of highly halogenated dioxins and furans initiated the elimination of chlorine from pulp
bleaching. Its application today in pulp bleaching is limited to small, old pulp mills in exotic regions. Current bleaching
processes use basically two alternative approaches: The replacement of chlorine by dominantly chlorine dioxide is labeled as
ECF (elemental chlorine free) bleaching. Total chlorine free (TCF) bleaching requires a complete change in technology. TCF
bleaching uses mainly oxygen and hydrogen peroxide for bleaching. Ozone or peracetic acid is in addition required to
achieve high brightness. In ECF bleaching the simplest approach is to just exchange chlorine with chlorine dioxide. The
optimization of an ECF sequence requires additional changes: higher temperature in the D stage and the reinforcement of
the extraction stages with oxygen and hydrogen peroxide. ECF “light” is a label used to describe a sequence using less
chlorine dioxide and more hydrogen peroxide.

Typical industrial bleaching sequences are listed in Table 4.

Table 4. Chemical pulp bleaching sequences

Pulp type Bleaching process sequence

Kraft pulp, softwood ECF ODEopDEpD, ODEoDnD

Kraft pulp, softwood ECF “light” OQ(OP)DP
Kraft pulp, softwood TCF OQ(OP)QPP, OOQ(OP)PaaP
Kraft pulp, hardwood ECF OD(hot)EopDP, O(ZE)DP
Kraft pulp, hardwood TCF OQPPP
Sulfite pulp TCF OQP, OQ(PaaP), EopP

In bleaching kraft pulp, oxygen is used to decrease the amount of residual lignin without loss of viscosity and strength.
Because kraft pulping and oxygen delignification both use sodium hydroxide as alkali source, combined evaporation and
recovery of the effluents from pulping and oxygen delignification is possible. Thus, oxygen delignification not only decreases
the amount of bleaching chemical required, it also lowers the overall effluent load. Oxygen delignification has become the
standard measure for lowering the lignin level after pulping. Softwood kraft pulp can be further delignified by more than 50 %,
and hardwood pulp by nearly 40 %.

The changes in bleaching technology have resulted in significantly lower levels of halogenated compounds in the effluent of
pulp bleaching. These compounds are determined as AOX (adsorbable organic halogenated compounds). Historically the
amount of AOX discharged per tonne of pulp could be higher than 5 kg/t. Most countries have set narrow limits to the
discharge of AOX. ECF bleaching allows staying within these limits as it generates much less halogenated compounds,
which show in addition improved biodegradability.

Combination of two bleaching chemicals in one stage is sometimes possible and advantageous. The effects of oxygen and
hydrogen peroxide, for example, are to a certain extent additive. Chlorine dioxide and ozone can be applied in one combined
step by using two mixers in line.

Water consumption in pulp production has decreased significantly. Volumes declined from more than 50 m3/t to about 15 m3
/t in modern pulp mills. The limitation to further decreases is the presence of “nonprocess elements” in wood. The recovery of
the process chemicals in parallel results in an increase of the concentration of these elements in the system. Therefore,
discharge of effluent or solids will still be necessary. The cations are predominantly traces of metals such as Ca, Mg, Fe, Mn,
and Cu. Chloride and sulfate are the main counterions. The target of process improvements is to minimize the impact not
only of the discharge of liquid effluent but also to decrease atmospheric emissions and the amount of solid waste disposed of
in landfills.

Bleaching chemicals are typically applied under medium-consistency conditions, that is, a fiber/water ratio of 1/9 to 1/11. This
relatively thick mixture is fluidized by special pumps and pressed through upflow towers.

Typical market pulp brightness for ECF softwood pulp is 88 – 90 % ISO. Hardwood pulp is sold at a brightness of 90+ % ISO.
Specialties such as photo paper can have a brightness > 92 % ISO. Lower brightness can be sufficient for a wide number of
applications in papermaking and tissue production, and thus brightness varies over a wide range from unbleached to
semibleached to fully bleached pulp. Typically TCF pulp is available with more brightness variation to balance brightness
requirements and fiber strength properties. In TCF bleaching it is more difficult to simultaneously obtain top brightness and
top fiber strength.

Special paper grades such as bank notes, cigarette papers, and tea bags are produced from special fibers. Esparto grass,
hemp, flax, kenaf, ramie, and abaca are applied, as well as cotton linters. Although not all these fibers can be bleached to
very high brightness, the requirement for bleaching chemical is low, and only short bleaching sequences are necessary.
Another group of annual fiber plants includes the cereals, especially rice straw, bamboo, and depithed bagasse. They are
used as a raw material for chemical or mechanical pulp.

4.1.2. Mechanical Pulp

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Grinding tree trunks on rotating grinder stones is the traditional method of preparing mechanical pulp. The abbreviation
describing this process is GW (groundwood) or PGW (pressurized groundwood) for processes operated at 2 – 3 bar. Today
rotating metal disks, refiners, and wood chips as raw material are widely used; the conventional groundwood process has
been phased out because of its high requirement for workforce. There are several slightly different processes: refiner
mechanical pulp (RMP), thermomechanical pulp (TMP), chemothermomechanical pulp (CTMP), and alkaline peroxide
mechanical pulp (APMP). In all cases, the amount of lignin in the pulp is reduced only slightly. At high temperature internal
bonding within the wood chips decreases and longer fibers result from the mechanical action. Pretreatment of the wood chips
with sodium sulfite, caustic soda (applied to softwood, e.g., spruce) or alkaline hydrogen peroxide (typically applied to
hardwoods such as aspen or poplar) yields a defiberized product with even longer fibers.

The use of strong oxidizing agents such as oxygen or chlorine dioxide for bleaching mechanical pulp would result in an
enormous consumption of chemicals and significantly lower the yield, because these chemicals would oxidize and dissolve
the lignin present in the pulp. Hydrogen peroxide is used because it predominantly destroys chromophores without attacking
the aromatic rings of lignin [7], so that yield losses are moderate. The amount of dissolved wood material depends on the
intensity of bleaching; the more peroxide is applied, the more alkali is required for its activation, and in turn more organic
material is dissolved. A simple possibility for a moderate increase in brightness is reductive treatment with sodium dithionite.
This chemical can be added already during the refining process.

The maximum possible increase in brightness is lower for mechanical pulps than for chemical pulp. Softwood mechanical
pulp can be bleached with dithionite to 70 – 75 % ISO. Hardwoods such as poplar and aspen bleach more easily, as their
lignin contents are lower. Thermomechanical pulps give lower brightness increases, because the chromophores produced by
high-temperature treatment are more stable towards reduction. Hydrogen peroxide bleaching produces higher brightness
levels: softwood pulp can be bleached to 75 – 80 % ISO. Hardwoods mechanical pulp can reach brightness levels of up to
85 % ISO.

Hydrogen peroxide bleaching is best conducted at high pulp consistency, preferably above 30 %. At high consistency the
relative concentration of the bleaching chemical is higher, and side reactions with organic compounds dissolved in the water
are avoided. Bleaching processes are run continuously in downflow towers. Reductive dithionite bleaching is carried out
conventionally at lower consistencies (4 – 6 %) in upflow towers to avoid consumption of the reducing agent by atmospheric
oxygen. Deaeration in modern medium-consistency pumps allows reductive bleaching to be carried out at medium
consistency (ca. 10 %) in upflow towers.

4.1.3. Paper Recycling (Deinking)

The amount of wastepaper recycled with a deinking step is continuously increasing. The aim of deinking is the removal of
printing ink and other impurities from the fibers. Typically, printing inks cannot be bleached, as they consist mainly of
pigments like carbon black and hydrophobic polymers. These inks must be removed mechanically. There are two major
processes: washing and froth flotation [13]. For froth flotation, repulping is carried out under alkaline conditions with the
addition of a sodium soap. The ink is detached and collected on precipitated calcium soap particles. The flotation of these
precipitates removes not only ink particles but also other impurities. The addition of hydrogen peroxide prevents alkaline
yellowing and improves brightness. As another additive sodium silicate is applied. It improves ink separation and suppresses
the coflotation of fillers and fines. For best brightness and highest yield all four chemicals — caustic soda, soap, hydrogen
peroxide, and sodium silicate — are required.

For deinking by washing, repulping of the wastepaper can be performed under alkaline or neutral conditions. To facilitate ink
detachment surfactants or soaps are added. The washing process removes ink, fillers, and fines simultaneously. It is
therefore the preferred method for the use of secondary fiber in tissue production.

Today the majority of recovered fibers subjected to a deinking process are used in newsprint production, where up to 100 %
of the final product can be recycled paper. In smaller amounts deinked wastepaper is used as furnish in higher quality paper
grades, such as SC (supercalendered) paper, copy paper, or printing and writing grades. Higher quality wastepaper (e.g.,
mixed office wastepaper) is used for the production of tissue paper grades. Brightening, especially the removal of dyes from
colored paper grades, includes a combination of reductive and oxidative bleaching with formamidine sulfinic acid and
hydrogen peroxide. A typical North American development is deinked market pulp of very high brightness. The intention of
the recovery procedures is to achieve a fiber quality close to short-fiber chemical pulp. This requires a multistage process,
including flotation, washing, and bleaching. The raw material generally is mixed office wastepaper. Bleaching stages include
oxygen, hydrogen peroxide, and sodium dithionite or formamidine sulfinic acid. In some mills hypochlorite is still used. A
higher content of mechanical fiber in such a process is difficult to handle, as oxygen delignification dissolves most of the fiber
material and, in parallel to the loss of yield, a very high effluent load is generated.

4.1.4. Environmental Aspects of Pulp Bleaching

Bleaching removes part of the product being bleached. Washing is the most important method for removing the oxidized or
reduced compounds and causes an effluent load which can be expressed as BOD or COD, or TOC (total organic carbon).
Authorities normally set limits to the discharge of biodegradable compounds and oxidizable material. Treating the effluent
starts with a “primary” step, the sedimentation of suspended solids (e.g., fibers). The standard method for removing organic
material from the effluent in kraft pulp mills is biological treatment in aerated lagoons. This is denoted “secondary” treatment.
The degradation of organic material with bacteria requires oxygen. Energy demand for aeration is about 1 kW·h/kg BOD5
[14]. About half of the organic material is transformed into carbon dioxide, and the other half becomes biomass and must be
separated as sludge. Sludge dewatering and disposal or combustion cause additional costs. An attractive alternative is an
anaerobic fermentation step. This conversion leaves only about 5 % of the organic matter as residue for disposal. All other
organic material is converted to biogas, mostly methane. Typically the BOD is decreased by more than 90 %. Anaerobic and
aerobic treatment can be combined in two successive stages starting with the anaerobic treatment. The excess sludge from
the aerobic stage can be recycled into the anaerobic stage. A “tertiary” treatment is the final precipitation of remaining
suspended or dissolved compounds with chemical coagulation. Usually, compounds for such a treatment are aluminum salts,
FeIII salts, and lime slurries. Tertiary treatment is mainly applied to remove excess nutrients like phosphorous, but it can also

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remove COD and AOX.

In ECF bleaching halogenated compounds are produced during the bleaching reaction. Because of the wide range of
halogenated products, the use of a sum parameter is widely accepted to characterize the amount. A standard method is AOX
analysis, which describes the amount of adsorbable (on activated carbon) halogenated compounds [8]. Conventional
bleaching resulted in AOX amounts of 5 – 8 kg/t of organically bound chlorine. ECF conditions can lower the AOX discharge
from the bleaching plant to less then 1 kg. A further decrease is achieved in biological treatment, which can cut the AOX level
by more than 50 %.

The bleaching process leaves residual halogenated organic compounds in the pulp, which are measured as organic halogen
(OX) in pulp. To a certain extent it is possible to identify the bleaching process applied by measuring the residual OX content
of a pulp sample. ECF bleaching has residual OX contents between 150 and 30 g/t. This lower level is also the accepted
level for TCF bleached pulp, because the pulp can have a natural background content of halogenated compounds and a
higher level of chloride ions in pulp during bleaching can generate residual OX even with TCF bleaching.

In chemical pulp production specific water consumption is below about 30 m3/t . A further decrease to less than 15 m3/t is
achieved with sophisticated washing equipment and countercurrent waterflow [15]. Complete bleach plant closure is very
difficult to achieve. Most units labeled as “closed” in reality are still consuming water. One reason are the “nonprocess”
elements present in wood. They become concentrated in the recovery loops and can cause equipment scaling or even upset
the recovery procedure. The inclusion of bleach plant effluent in the recovery process increases scaling and corrosion
potential. Consequently “closed” mills use “kidneys” to eliminate troublesome substances. Such purging consumes water or
requires the disposal of solid waste after evaporation and combustion. (Solid waste would contain salts of the nonprocess
elements and salts resulting from pulping and bleaching chemical application).

Totally effluent free bleaching only changes the kind of discharge: from water pollution to air pollution or to the need for solid
waste disposal. The concentration process required (evaporation) will increase energy demand.

4.2. Textile Fibers ( Textile Dyeing)

The quality of the raw material dictates the potential for a simple or a more complicated bleaching procedure. The higher the
level of impurities in the material to be bleached, the more steps are required. Natural products like cotton, flax, and wool can
be heavily contaminated with sand and other dirt. Washing in the presence of acid or chelating agents may be required to
achieve good results in the bleaching stage.

Cotton, the most important natural fiber, is usually bleached with hydrogen peroxide because alkaline oxidation not only
increases brightness but also removes extractives, saponifiable waxes, and pectins, and destroys the lignin of residual seed
capsules. In the peroxide stage, chelating agents, magnesium salts, and sodium silicate are added to prevent transition metal
catalyzed destruction of the cellulose.

Cotton linters are used as a specialty fiber for papermaking and as raw material for cellulose derivatives like cellulose
acetate. Linters are normally alkaline pretreated and then bleached in several stages, for example, in a chlorine dioxide –
hydrogen peroxide – chlorine dioxide sequence, analogous to chemical pulp bleaching.

Flax is the source plant for linen. Bleaching of flax is very similar to that of other plants containing bast fibers, for example,
hemp or ramie. Because of the low lignin content a pulping process is not required. Most of the impurities can be removed by
mechanical action. High brightness and cleanliness is achieved with multistage processes using a hot alkaline pretreatment
followed by sodium chlorite and hydrogen peroxide.

Wool needs thorough washing after shearing. The scouring step removes sand and other dirt and separates lanolin (wool
fat). Wool is a keratin (protein) fiber and thus sensitive to alkaline treatment. Hydrogen peroxide bleaching must be carried
out at low temperature and below pH 8, often under neutral to even slightly acidic conditions. As a result the bleaching times
are long and the potential for high brightness is limited. Combining oxidative peroxide treatment and reductive dithionite
treatment gives the greatest increase in brightness.

Synthetic fibers like rayon are bleached with hydrogen peroxide or hypochlorite. Because polyurethane is sensitive to
chlorinating chemicals, polyurethane fibers are bleached only with hydrogen peroxide. Polyamides, polyesters, and
polyacrylonitriles are bleached with sodium chlorite. Hot alkaline hydrogen peroxide may cause polyamides to lose strength.

4.3. Other Products

Animal Products. Similar to wool hair and bristle are bleached with semineutral or slightly alkaline peroxide.

Mother-of-pearl, ivory, and bones are bleached with hydrogen peroxide solutions, which are stabilized with either sodium
diphosphate in weak alkaline medium or sodium silicate, possibly in the presence of ammonia. Bones and ivory are bleached
at room temperature for an extended time.

Vegetable Products. Straw is bleached with alkaline hydrogen peroxide. Straw-hat bleaching was the first important
application for sodium peroxide at the beginning of the 1900s. Exotic straws such as pandan straw or bamboo grass require
bleaching with sodium chlorite. The bleached products are typically used by florists.

Peeled rattan reeds, which are used for wicker baskets and furniture, are brightened with hydrogen peroxide (buffered with
sodium carbonate and silicate) at ambient temperature and a dithionite stage.

Wood veneer and wood are bleached with hydrogen peroxide and ammonium carbamate. Offcolors can be corrected with
this treatment, which is important in furniture production.

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Palm oil and other vegetable oils for food and chemical production need to be purified before use. They are typically
bleached not by a chemical reaction but by adsorption of colored impurities. High surface area clays (aluminum or
magnesium silicates) are added at elevated temperature. Filtration is used for separation. The same procedure is applied for
paraffins and waxes. Disposal of the clay contaminated with oil and colored material can become an environmental
challenge.

Inorganic Products. Clays are bleached as aqueous slurries with sodium dithionite to remove the color resulting from metal
ions such as iron. The reduced metal (Fe2+) is washed off.

Technical-grade sulfuric acid is bleached with hydrogen peroxide. The oxidation of organic impurities takes place via the
intermediate generation of Caro's acid (H2SO5).

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References
1. C. W. Dence, D. W. Reeve (eds.): Pulp Bleaching: Principles and Practice, Tappi Press, Atlanta 1996.
2. H. Sixta: Handbook of Pulp, Wiley, New York 2006.
3. M. Peter, H. K. Rouette, Grundlagen der Textilveredlung, Deutscher Fachverlag, 1989.
4. Prüfung von Papier Pappe Zellstoff und Holzstoff, Band 1: Chemische und mikrobiologische Verfahren, Springer Verlag
1991; Band 2: Mikroskopische und photometrische Verfahren, Springer Verlag 1993; TAPPI Test Methods, TAPPI Press
1996, Atlanta.
5. ISO 2470-1973, Tappi T 646 om-86, DIN 53 145.
6. A. Maréchal, J. Wood Chem. Technol. 13 (1993) 6, 91.
7. J. Gierer, Holzforschung 36 (1982) 55. Links
8. DIN 38409 H 14.
9. K. Kringstad, K. Lindström, Environ. Sci. Technol. 18 (1984) no. 8, pp. 236A – 238A. Links
10. K.-E. L. Eriksson: Biotechnology in the Pulp and Paper Industry, Springer, Berlin 1997.
11. R. Bourbonnais, M. G. Paice, “Enzymatic Delignification of Kraft Pulp using Laccase and a Mediator”, Tappi J. 79 (1996)
199. Links
12. Glossary of Bleaching Terms, Bleaching Committee, Technical Section, CPPA, Montreal, QC Canada.
13. Papermaking Science and Technology, Book 7, “Recycled Fiber and Deinking”, Fapet Oy, Helsinki 2000.
14. C. H. Möbius: Abwasser der Papier- und Zellstoffindustrie, 3. Auflage, 2002, revised Dec. 2005, available at: www.cm-
consult.de.
15. G. Annergren, P. Sandström, “A Bleach Plant Designed for Closure”, Papier 50 (1996) V12 – V16. C.-J. Alfthan, L.
Ahlenius, G. Svensson, “Betriebserfahrung bei der Herstellung von Sulfatzellstoff im geschlossenen Bleichkreislauf”,
Papier 50 (1996) V8 – V12.
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