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8.2 Reactions between Pulp Constituents and Aqueous Sodium Hydroxide Solution 935

to originate from alpha-cellulose by degradation during the pulping and bleaching

processes.

The composition of the beta- and gamma-celluloses fractions removed from the

wood pulp during cold and hot extraction processes with respect to the amount of

unchanged carbohydrates has been the focus of few studies. Corbett and Kidd

studied the degradation of a mixture of beta- and gamma-celluloses extracted by

hot alkali from spruce pulp [11]. These authors found that the insoluble residue

essentially consists of glucan, and whereas the beta-cellulose fraction is made predominantly

of xylan, the gamma-cellulose originates from a mixture of glucan

and mannan. In a recent study, the change in composition of the alpha- (residue),

beta- and gamma-celluloses fractions created during treatment of a beech sulfite

dissolving pulp with aqueous NaOH of various concentrations ranging from 20 to

340 g L–1 at 20 °C, 50 °C and 80 °C, was investigated [12]. The pulp consistency was

kept constant at 5%, which is a typical value for the industrial steeping process.

The profile of the xylan content of the residue (alpha-cellulose) and the weight

fraction of the dissolved hemicelluloses (sum of beta- and gamma-cellulose)

related to the initial amount of pulp is illustrated graphically in Fig. 8.1.

As expected, xylan removal is more efficient at 20 °C than at higher temperatures.

To obtain the lowest possible xylan content in the pulp residue (about 0.7%

appears to be alkali-resistant), the NaOH concentration must be increased from

0 100 200 300

0

1

2

3

4

5

0 100 200 300

0

3

6

9

12

15 20 .C 50 .C 80 .C

Xylan content [%od]

Dissolved

Hemicellulose [% od]

NaOH concentration [g/l]

Fig. 8.1 Profiles of xylan content in the pulp

residue (upper) and the amount of dissolved

hemicelluloses (sum of beta- and gamma-cellulose)

(lower) during alkaline treatment of a

beech sulfite dissolving pulp (93.4%R18, 4.0%

xylan) at different temperatures [12]. Caustic

treatment: 5%consistency , 30 min reaction

time, NaOH concentrations: 20, 40, 60, 80,

100, 140, 180, 280, and 340 g L–1.

936 8 Pulp Purification

8.2 Reactions between Pulp Constituents and Aqueous Sodium Hydroxide Solution

100 g L–1 to about 140 g L–1 when raising the temperature from 20 to 50 °C. The

alkaline treatments at 50 °C and 80 °C reveal a comparable pattern of xylan

removal up to a lye concentration of about 280 g L–1. The xylan removal efficiency

remains unchanged at 80 °C and also at NaOH concentration up to 340 g L–1, but

is slightly reduced at lower temperatures.

The profile of the amount of hemicelluloses dissolved during alkaline treatment

resembles the swelling behavior of cellulose in dependence on lye concentration,

as experienced by Saito [13,14]. At low temperature (20 °C), the amount of dissolved

hemicelluloses increases rapidly with increasing NaOH concentration, and

passes through a maximum at 100 g NaOH L–1. While the residual xylan content

remains fairly constant with increasing lye concentration, the amount of dissolved

hemicellulose decreases significantly to values less than half of the amount determined

at maximum solubility. In the low lye concentration range up to 170 g

NaOH L–1, the solubility of pulp constituents is significantly lower at 50 °C as compared

to 20 °C, whereas the maximum solubility is shifted to 140 g NaOH L–1. At

higher NaOH concentrations, the pattern of the solubility of hemicelluloses develops

quite comparably for both temperatures, 20 °C and 50 °C, respectively. In contrast,

alkaline treatment at 80 °C causes a steady increase in hemicellulose solubility

up to a NaOH concentration of 280 g L–1. Beyond this lye concentration, the

amount of dissolved hemicelluloses experiences a slight reduction (see Fig. 8.1,

lower). In hot alkali treatments (80 °C), the removal of short-chain carbohydrates