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8 Pulp Purification

Is calculated as effective alkali (ea). Assuming total ea losses (including ea consumption

through CCE treatment and washing losses of about 50 kg odt–1), an

amount of 616 (equals 666–50) kg odt–1 of EA is recycled to the cooking plant

(note that the CCE filtrate must be evaporated in order to reach the white liquor

EA-concentration). Supposing a bleached yield of 35% (o.d.), this amount of alkali

corresponds to an EA charge of 216 kg odt–1 wood which, for cooking, seems to be

a rather too-low than a too-high amount (depending on the wood species, cooking

technology and intensity of prehydrolysis, the required EA amount for cooking

ranges from 22% to 26% on o.d. wood). This brief example shows that the excess

lye of cold alkali purification balances quite well with the demand in PHK cooking.

However, the situation is different when combining acid sulfite cooking with

a CCE treatment. There, the opportunities to re-use the excess lye quantitatively

are limited to special cases. For example, one possibility of disposing of the excess

lye from the CCE treatment would be to use it for hot caustic extraction, provided

that the production of hot alkali-purified pulp considerably exceeds that of cold

alkali-purified pulp. If this is not the case, the only chance of preventing too-high

losses of alkali would be to recirculate the pressed lye to the sodium hydroxide

circuit for re-use in CCE treatment. A closed loop operation, however, inevitably

leads to an accumulation of dissolved hemicelluloses in the lye circulation system.

Depending on the amount of hemicelluloses removed from the pulp and the leaks

from the circuit (e.g., the discharge with the press cake), a certain level of dissolved

hemicelluloses is allowed to be reached under equilibrium conditions. It

has been reported that the extent of purification is much deteriorated by the presence

of dissolved hemicelluloses and other impurities [4]. Surprisingly, if an (E/O)

treated hardwood acid sulfite dissolving pulp is subjected to mild cold caustic

extraction at 5% NaOH concentration in the presence of 10 g L–1 hemicelluloses,

the xylan content even slightly increases, clearly due to xylan reprecipitation

(Fig. 8.9).

As expected, the purification efficiency increases when raising the NaOH concentration

to 90 g L–1 while keeping the ratio to the hemicellulose concentration

constant at 5:1. Nonetheless, the presence of hemicelluloses significantly impairs

pulp purification (see Fig. 8.9). In the light of the previous discussion about the

nature of hemicelluloses, it was interesting to examine which of the two hemicellulose

fractions would have the greater impact on purification efficiency. The

gamma-cellulose fraction was separated by nanofiltration, while the beta-cellulose

was prepared by precipitation upon acidification. The data in Fig. 8.10 show that

the presence of the low molecular-weight gamma-cellulose fraction during CCE

treatment does not affect purification, whereas the presence of the high molecular-

weight beta-cellulose clearly impedes xylan removal.

This observation strengthens the presumption that xylan, when exceeding a certain

molecular weight, precipitates onto the surface of the pulp fiber even at rather

high NaOH concentration (2.5 mol L–1). Xylan redeposition is clearly the main reason

for a reduced purification efficiency, if CCE is carried out with a lye containing

dissolved beta-cellulose.

946

8.3 Cold Caustic Extraction

0 20 40 60 80 100

0.0

1

2

3

hemicellulose containing lye: 10 g/l at 50 g NaOH/l; 18 g/l at 90 g NaOH/l

pure lye

Xylan content [%]

NaOH concentration [g/l]

Fig. 8.9 Effect of hemicelluloses in the lye on the xylan

removal efficiency during CCE treatment of hardwood acid

sulfite dissolving pulp (HW-S) in the range of 0 to 100 g L–1

NaOH [28]. HW-S: (E/O) pretreated, kappa 1.6, 2.7%xylan.

pure Lye 20 g/l Gamma 20 g/l Beta

0.0

0.5

1.0

1.5

2.0

Xylan content [%]

Lye Purity

Fig. 8.10 Effect of the presence of low (gamma) and high

(beta) molecular-weight hemicelluloses on xylan removal efficiency

during CCE treatment of hardwood acid sulfite dissolving

pulp (HW-S) at 100 g L–1 NaOH and 25 °C [28].

Unbleached HW-S: kappa number 5.7; total bleaching

sequence: CCE (E/O)ZP.

947

8 Pulp Purification

8.3.4

Placement of CCE in the Bleaching Sequence

The efficiency of cold alkali purification is reported to be improved by a preceding

hot caustic extraction stage in the case of a sulfite dissolving pulp [4]. More

recently, it has been shown that the position of the CCE stage within a bleaching

sequence has no significant impact on the degree of purification, provided that

washing takes place between both purification stages (Fig. 8.11). In contrast,

when oxygen delignification (O) follows hot caustic extraction (E) without interstage

washing, denoted as (E/O) sequence, a CCE treatment preceding (E/O)

seems to be advantageous over the reversed sequence with respect to delignification,

as illustrated in Fig. 8.11. The simple reason for the higher overall delignification

efficiency of the latter is that unbleached pulp exhibits a higher level of

alkaline-extractable lignin than an (E/O) pretreated pulp, while the efficiency of

oxygen delignification appears to be unaffected by the prehistory of pulp treatment.

Likewise, the position of CCE within a final bleaching sequence of a hardwood

TCF-bleached PHK pulp proved to have no influence on the purification efficiency,

as shown in Fig. 8.12. Nevertheless, placing CCE before the ozone stage

(Z) is preferred compared to both other alternatives because of a loss in viscosity

(in the case of CCE after Z) or higher capital costs (in the case of CCE after P).

Moreover, CCE treatment on the bleached pulp might be disadvantageous with

Untreated (E/O)-CCE CCE-(E/O)

0

1

2

3

4

Kappa number