Chapterm 3:

Chemistry of Chemical Pulp Bleaching

1. Introduction
Multi-stage bleaching sequences are customarily divided into delignification and
bleaching segments. In a typical delignification
sequence, the bulk of the residual lignin in a chemical pulp is degraded and
solubilized by a single oxidant or combination of oxidants such as chlorine,
chlorine dioxide,oxygen, hydrogen peroxide, and ozone in conjunction with joint
or sequential alkali (NaOH) treatments. Oxidative processes invariably lead to the
formation of acidic groups (carboxylic, phenolic and enolic) that lend enhanced
water and alkali solubility to the lignin fragments to which they are attached.
Depending on the bleaching chemical and.the residual lignin content of the pulp,
some bleaching may accompany delignification.
In the bleaching segment of a multi-stage bleaching sequence, oxidants such as
chlorine dioxide. sodium hypochlorite, and hydrogen peroxide are used to
remove the remainder of chromophore systems initially present in the lignin and
those formed
in preceding pulping and prebleaching treatments. Because at this juncture of a
multi-stage bleaching sequence the concentration of non-carbonhydrate material
in the pulp is relatively low, it is essential that the bleaching (oxidizing) agent
selectively eliminate chromophore residues while leaving the carbohydrate
components relatively intact to preserve pulp strength and yield.
Any attempt to describe delignification and bleaching phenomena by a set of
welldefined chemical reactions is of necessity
limited by the meager amount of information available dealing with the structure
of lignin in unbleached pulps or in partially
delignified or bleached pulps.
The situation is further complicated by the fact that most of the oxidant systems
used to delignify or bleach pulp consist of mixtures of active species each of
which is a potential contributor to the bleaching process. These obstacles have
necessitated the ensuing descriptions of the chemistry of the different bleaching
chemicals being restricted to the initial treatment of unbleached pulps with
oxidant and alkali because only in pulps of this type is the structure of the
residual lignin known with any reasonable degree of certainty (see Chap. III 1).
Although the main emphasis in this chapter is on the chemistry of delignification
in bleaching, discussion of the reactions of carbohydrates and extractives with
various oxidizing agents and alkali is included
below in cases where the outcome of a bleaching treatment is affected by their
occurrence.\

2. Reactions of lignin with bleaching agents and alkali

2.1 Chlorine
Reaction species in the chlorine-water system
The principal active chemicals in an aqueous chlorine solution are elemental
chlorine and hypochlorous acid. In bleaching, the relative amounts of these
chemicals are determined mainly by the elemental chlorine and hydrogen ion
concentrations in accordance with the equilibrium relationship.
Cl, + H,0 <--> HOCl + W + Cl [1]
Under typical pulp chlorination conditions, elemental chlorine and hypochlorous
acid are present initially in approximately equal amounts (1). As the chlorination
proceeds, the pH decreases because of the formation of hydrochloric and organic
acids. As a result, the [Cl,]/[HOCl] ratio increases in accordance with the
equilibrium expressed by equation [ 1]. Although the reactions of chlorine and
hypochlorous acid with lignin are qualitatively similar, their relative contributions
to the overall reaction comprising the chlorination process may vary significantly
depending on the reaction conditions. For example, a decrease in the initial
chlorina- lion pH enhances the delignification of softwood kraft pulp by
increasing the proportion of elemental chlorine (2).Other reactive species that
may play a role in chlorination are chlorine radicals (3) and dichlorine monoxide
(4). The proposed minor involvement of chlorine radicals in bleaching is based on
the detection of a dimeric coupling product after the chlorination of guaiacol (5)
and on the effect of known radical scavengers such as chlorine dioxide and
sulfamic acid in controlling the viscosity loss (6) proposed to result from attack
of chlorine radicals on cellulose (7). Dichlorine monoxide is formed by the
dehydration ofhypochlorous add (4):
2 HOCl <--> qo + H,0 [2]
The involvement of this reactive compound in pulp chlorination has not been
demonstrated. In their reactions with lignin and other pulp constituents,
elemental chlorine and hypochlorous acid function as electrophiles (8 and Table
1 in Chap. m 2). The initial reacting species in this instance is a chloronium ion
(Ci+) formed by the heterolytic cleavage of the Cl-Cl bond in elemen-1 (Av
HC-R /a•ta! chlorine and the 0-Cl bond in the conjugate acid of hypochlorous
acid: HOC! + W <--> H,OCl - H,0 + Ci+ [3]

Substitution reactions
Hydroxyl- and alkoxy-activated aromatic nuclei in lignin undergo rapid and
extensive substitution by chlorine. Thus, in the chlorination of a softwood kraft
pulp, substitution of nearly 2 Cl/C9 unit has been observed after only five
minutes' reaction (9). Most, if not all, of this chlorine uptake can be attributed to
aromatic substitution. !hi reaction is portrayed mechanistically
m Fig. lA. The number and location of aromatic chloro substituents in chlorinated
lignin depend on the amount of chlorine
applied and the number and type of substituent groups initially present.
Uncondensed guaiacyl nuclei in softwood lignin have three unsubstituted sites
available for chlorine substitution; syringyl nuclei, typical of hardwood lignin,
have but two. An
additional chloro substituent can be introduced into each of the foregoing ring
types by electrophilic displacement of a suitably
substituted side chain (see below). Under conventional chlorination conditions,
chlo- R = H, Alkyl, Aryl ,, OCH, ,,.....a R,R1 = H or rest of lignin molecule -W ci HLo """ /
OCH, ,,.....a R,
Fig. I. Reactum sequences for aromatic nbstihltlon and side chain displacement
lry cbloronlum ums.