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8.4Hot Caustic Extraction 955

92 94 96 98

70

80

90

100

HW-Sulfite SW-Sulfite:

E-stage EO-stage (E/O)-stage E-stage

Purification yield [%]

R18 content [%]

Fig. 8.18 Purification yield as a function of R18 content comparing

E-, (EO)-, and (E/O)-treatments of hardwood sulfite

dissolving pulp (HW-S) and E-treatment of spruce sulfite

dissolving pulp (SW-S) [33]. Pulps and conditions are as in

Fig. 8.17.

Tab. 8.3 Specific yield losses and NaOH consumption values in

the course of E-, (EO), and (E/O) treatments of beech and

spruce sulfite pulps.

Pulp Purification Yield loss per 1%

R18 increase

NaOHcons per

C6 sugar dissolved

<96% >96% <96% >96%

[% o.d. pulp] [mol mol–1]

HW-S E 3.7 5.0 1.4 1.6

HW-S EOa 4.0 2.0

HW-S (E/O) 3.2 5.0 2.0 2.0

SW-S E 3.3 4.1 1.4 1.6

a. Max. 95% R18.

the alkali consumption in pure E stages amounts to between 1.4 and 1.6 mol mol–1

monosaccharide unit (calculated as C6) dissolved, indicating that the end products

of degradation must be fragmented to smaller units than isosaccharinic acid, such

956 8 Pulp Purification

as glycolic, lactic, pyruvic and 3,4-dihydroxybutyric acids, as described by MacLeod

and Schroeder [34]. As anticipated, specific alkali consumption increases to a value

of about 2 mol mol–1 monosaccharide unit when oxygen delignification is integrated

Into the purification reaction, either in the same (eo) or in a separate stage

(E/O).

An elevated temperature between 80 and 120 °C is necessary to activate peeling

reactions in the presence of sufficient alkali to achieve an increase in R18 and

R10, and a decrease in hemicelluloses. As shown in Fig. 8.19, cellulose degradation

begins at temperatures exceeding 140 °C, as suggested by a decrease in R10

content, indicating the fragmentation of microfibrils. Clearly, temperatures

beyond 140 °C do not contribute to further purification due to alkaline hydrolysis.

0 2 4 50 100 150

80.0

86

88

90

92

94

96

98

R18 R10

R values [%]

Temperature [.C]

Fig. 8.19 Development of R18 and R10 contents as a function

of temperature of a high-viscosity spruce sulfite pulp during

HCE [4]: HCE-conditions: 120 kg NaOH odt–1, 4 h.

8.4.1.2 Xylan versus R18 Contents

Prolonged acid sulfite cooking causes both the removal of hemicelluloses (e.g.,

xylan) and the degradation of cellulose, resulting in a low-viscosity pulp. HCE

treatment of low-viscosity sulfite pulps allows reduction to a very low xylan content,

while the R18 content remains rather close to that of pulps with a higher

initial viscosity at a comparable yield level (Fig. 8.20). These data conclude that the

R18 content of medium- to high-viscosity pulps partly contains alkaline-stable

hemicelluloses. On the other hand, part of the degraded cellulose is not included

in the R18 fraction of the low-viscosity pulp.

8.4Hot Caustic Extraction 957

81 84 87 90 93

92

93

94

95

96

Xylan content [%]

Medium Viscosity: R18 Low Viscosity: R18

R18 content [%]

Purification yield [%]

1

2

3

4

Xylan Xylan

Fig. 8.20 R18 and xylan contents related to purification yield

during (E/O)-treatment of hardwood sulfite dissolving pulp

(HW-S) [33]. Low-viscosity pulp: viscosity 490 mL g–1, kappa

number 6.2, xylan content 4.5%; Medium-viscosity pulp: viscosity

730 mL g–1, kappa number 6.2, xylan content 6.5%.

1 2 3 4 5 6

89

90

92

94

96

Unbleached (E/O)-treatment:

Medium viscosity Low viscosity Medium viscosity Low viscosity

R18 content [%]

Xylan content [%]

Fig. 8.21 R18 versus xylan content during (E/O)-treatment of

hardwood sulfite dissolving pulp (HW-S) [33]. Low-viscosity

pulp: viscosity 490 mL g–1, kappa number 6.2, xylan content

4.5%; Medium-viscosity pulp: viscosity 730 mL g–1, kappa

number 6.2, xylan content 6.5%.

958 8 Pulp Purification

The distinct difference in the residual xylan contents of low- and medium-viscosity

hardwood sulfite dissolving pulps at a given R18 content is clearly shown in

Fig. 8.21. The xylan content of the medium-viscosity pulp is approximately 1%

higher than that of the low-viscosity pulp when compared at a level of 95% R18

(2.8% versus 1.8% xylan).

8.4.1.3 Purification versus Viscosity

The removal of short-chain carbohydrates through HCE treatment results in a

slight increase in viscosity because stepwise degradation (peeling) has only a small

effect on the molecular weight of long-chain cellulose. The effect of HCE on viscosity

has been expressed as a negative change of chain scissions for both spruce

and beech dissolving pulps to consider different levels of initial viscosity.

The data in Fig. 8.22 reveal a clear relationship between the degree of purification

and viscosity increase, reflecting the removal of short-chain material. The

change in viscosity is more pronounced for beech dissolving pulp, indicating that

the molecular weight of the removed hemicelluloses is lower than that from

spruce dissolving pulp. Alternatively, a greater amount of low molecular-weight

material is removed from the beech dissolving pulp during HCE treatment; this

suggestion would be in line with the higher specific yield loss when compared to

spruce dissolving pulp.

91 93 95 97

-1,6

-1,2

-0,8

-0,4

0,0

HW-Sulfite SW-Sulfite

Medium viscosity Medium viscosity High viscosity

Chain scissions, 1/DP

HCE

-1/DP

untreated

[*10-4 mol/AGU]

R18 content [%]

Fig. 8.22 Change in pulp viscosity, expressed

as negative number of chain scissions, as a

function of the degree of purification, characterized

as R18 content, during E-treatment of

hardwood and softwood sulfite dissolving

pulps (HW-S, SW-S) [33]. Medium-viscosity

HW-S: viscosity 590 mL g–1, kappa number 4.6;

Medium-viscosity SW-S: viscosity 625 mL g–1,

kappa number 4.6; High-viscosity SW-S: viscosity

890 mL g–1, kappa number 12.2.

8.4Hot Caustic Extraction 959

8.4.1.4 Purification versus Kappa Number and Extractives

Hot caustic purification also removes other pulp impurities such as lignin and

extractives. Most of the kappa number reduction occurs already at low NaOH

charge, and this can be attributed to a readily available lignin (Fig. 8.23). The

more alkali-resistant lignin is gradually decreased with increasing NaOH charge.

It may be speculated that part of the removed lignin is associated with the

extracted (and degraded) xylan.

0 30 60 90 120

2

3

4

5

E-treatment of HW-Sulfite Pulp

Kappa number

NaOH charge [kg/odt]

Fig. 8.23 Course of kappa number as a function of NaOH

charge during E-treatment of hardwood sulfite dissolving

pulps (HW-S) [33]. HW-S: viscosity 580 mL g–1, kappa number

5.1; E conditions: 90 °C, 240 min.

Hot caustic extraction is a very efficient stage in the removal of resin constituents

of sulfite pulps [27]. The saponification of fats, waxes and other esters is the

key reaction responsible for the removal of extractives. The removal efficiency can

be further enhanced by the addition of surfactants (nonyl phenol with attached

polyoxyethylene chain), and this may also solubilize the nonsaponifiables. The deresination

of softwood pulps with large amounts of resin can be further improved

by subjecting the pulp to increased mechanical forces that allow removal of the

encapsulated resin from the ray cells. A process developed by Domsjo involves the

use of a Frotapulper, along with the addition of caustic for the de-resination of sulfite

pulps (Fig. 8.24) [35,36].