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150 °C for 2 h, more than 70% of a xylan, which was added to the cooking liquor

(isolated from a eucalyptus pulp), was retained on the cellulose surface at a residual

effective alkali concentrations of approximately 10 g L–1, and still more than

20% In the case of alkali concentrations up to 50 g l–1 [67]. Xylan redeposition has

been demonstrated unequivocally by carbohydrate and GPC analysis (Fig. 11.24).

The xylan distributions across the fiber wall of TCF-bleached acid sulfite and

PHK dissolving pulps, obtained from both spruce and beech wood, were investigated

employing a new enzymatic peeling technique [69,70]. A general characterization

of the pulp substrates subjected to enzymatic peeling is provided in

Tab. 11.11.

1048

11.3 Dissolving Grade Pulp

3 4 5 6 7

0.0

0.3

0.6

0.9

1.2

Xylan added linters cooked without xylan linters cooked with xylan

dW/d(logM)

log Molar Weight

Fig. 11.24 Molar mass distribution of cotton linters after

cooking for 2 h at 150 °C with a residual EA-concentration of

10 g L–1 in the absence and presence of xylan [67]. The xylan

was isolated from a eucalyptus kraft pulp. GPC measurements

were made according to [68].

Tab. 11.11 Characterization of TCF-bleached dissolving pulps

made from spruce and beech wood produced by acid sulfite and

prehydrolysis kraft (PHK) cooking procedures [70].

Pulp type Bleaching

sequence

Bleached yield

[%]

Viscosity

[mL g–1]

Brightness

[% ISO]

Xylan

[%]

Glucomannan

[%]

Beech-S (E/O)-Z-P 39.7 573 91.4 3.3 0.6

Beech-PHK O-A-Z-P 38.1 465 91.1 6.4 0.4

Spruce-S (E/O)-Z-P 42.3 526 90.0 1.8 2.4

Spruce-PHK O-A-Z-P 38.5 439 83.4 2.3 1.3

The enzyme treatment causes a peeling effect which removes fiber material,

starting from the fiber surface. An analysis of the removed material by capillary

zone electrophoresis (CZE) revealed fundamental differences in the radial distributions

of hemicelluloses, as shown in Fig. 11.25. These differences may account

for some of the differences in dissolving properties of acid sulfite and PHK pulps.

The results show that all dissolving pulps investigated have a higher xylan content

In the surface layer than in the inner fiber wall. This is in agreement with

results obtained from paper-grade pulps [70,71]. The enrichment, however, is

1049

11 Pulp Properties and Applications

1 10 100

0

2

4

6

8

Sulfite: Spruce Beech

PHK: Spruce Beech

Xylan content in peelings [wt%]

Peeled carbohydrates [wt%]

Fig. 11.25 Radial distribution of xylan in TCF-bleached spruce

and beech sulfite and PHK dissolving pulps, according to

Tab. 11.11. Xylan content determined in aliquots of the hydrolyzate

(mass % of carbohydrates), collected after 1, 3, 10 min

and 48 h of enzymatic peeling, and after total hydrolysis [70].

highly dependent upon both the process and the wood species used. The high

Xylan content located in the outermost layers of the beech phk fibers suggests

that xylan precipitation occurs in the final kraft cooking phase, as shown for cotton

linters in Fig. 11.24. Beech sulfite dissolving pulp, however, shows a comparable

even cross-sectional concentration profile, as was determined for paper-grade

pulps [71]. For spruce PHK and acid sulfite dissolving pulps, only a very thin outermost

surface enrichment of xylan is found. But again, xylan is more enriched at

the surface of the PHK fibers as compared to the acid sulfite fibers. It is known

from practice that sulfite pulp behaves satisfactorily during the manufacture of

cellulose acetate, whereas kraft pulp with a similar (average) chemical analysis

does not. The enrichment of hemicellulose in PHK pulps may be one reason for

the impaired properties. Therefore, it is important to know if the pronounced

xylan profile through the cell wall can be leveled out by reinforced purification

conditions. Indeed, the enrichment of xylan was shown to decrease considerably

when prehydrolysis conditions were gradually intensified (increasing P-factor)

while the kraft cooking conditions were kept constant (Fig. 11.26).

A general characterization of the beech PHK pulps subjected to enzymatic peeling

is provided in Tab. 11.12.

1050

11.3 Dissolving Grade Pulp

50 500 1000 2000

0

10

20

30

40

50

60

Average Xylan Content [%]

at a peeling rate of 10 mass %

Xylan Enrichment on Surface [%]

P-factor

xylan enrichment

0

5

10

15

20

average xylan content

Fig. 11.26 Xylan enrichment on surface at a peeling rate of

10 mass % of beech PHK pulps prepared by increasing P factors

while Visbatch® cooking conditions were kept constant.

For enzymatic peeling conditions, see Fig. 11.25.

Tab. 11.12 Characterization of TCF-bleached beech PHK pulps

prepared according to the Visbatch® process comprising four

different levels of P-factor [72].

Pulp type Bleaching

sequence

Bleached yield

[%]

Viscosity

[mL g–1]

Brightness

[% ISO]

Xylan

[%]

Glucomannan

[%]

50 O-A-Z-P 44.4 466 90.7 15.6 0.6

500 O-A-Z-P 38.1 465 91.1 6.4 0.4

1000 O-A-Z-P 34.7 488 91.2 3.9 0.3

2000 O-A-Z-P 30.4 470 89.0 2.3 0.2

The decrease in surface xylan concentrationmay be explained by both the enhanced

removal of xylan from the outermost surface layers through reinforced prehydrolysis

conditions, and the diminished reprecipitation of xylan from solution during the

final phase of cooking due to a significant reduction in xylan concentration.