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8.3 Cold Caustic Extraction

Clearly, delignification is most pronounced for the unbleached pulp. However,

significant parts of the residual lignin structures are even removed after oxygen

delignification through CCE, but this may be attributed to the dissolution of xylan

linked to residues of oxidizable structures (degraded lignin and/or HexA?).

8.3.6

Molecular Weight Distribution

The aim of CCE is selectively to remove short-chain carbohydrates and other alkaline-

soluble impurities, and this leads to a narrowing of the molar mass distribution.

The effect of CCE on molecular weight distribution (MWD) has been investigated

using a standard hardwood sulfite dissolving pulp (HW-S). The data in

Fig. 8.14 show that the main part of the short-chain carbohydrates with molecular

weights ranging from 2.5 to 12 kDa (maximum at 5 kDa) is removed through

CCE. At the same time, the mid-molecular weight region between 30 and 380 kDa

becomes enriched. CCE treatment at low temperature (23 °C) proves to be rather

selective. Only a very small proportion of the very high molecular-weight fractions

(>1000 kDa) is degraded through CCE. Numerical evaluation of the MWD confirms

the removal of short-chain material (Tab. 8.2). It should be noted that the

polydispersity and amount of low molecular-weight fractions (below DP50 and

DP 200) are significantly decreased, while the high molecular-weight fraction

remains largely unchanged (beyond DP2000).

103 104 105 106 107

0.0

0.2

0.4

0.6

0.8

1.0

HW-S CCE treated HW-S Δ (CCE-Untreated)

dW/dlogM

Molar Mass [g/mol]

Fig. 8.14 Molar mass distribution of a hardwood-sulfite dissolving

pulp (HW-S) before and after CCE treatment [12].

CCE-treatment: 80 g L–1 NaOH, 23 °C, 45 min.

951

Tab. 8.2 Numerical evaluation of molecular weight distribution

of HW-S pulp before and after CCE treatment [12]. DP: degree of

polymerization, I: weight fraction.

Pulp DPw DPn PDI I< P50

[wt.%]

I< P200

[wt.%]

I> P2000

[wt.%]

HW-S 1950 245 8.0 5.1 17.4 27.9

HWS-CCE 1880 355 5.3 2.0 13.4 26.6

8.4

Hot Caustic Extraction

The purpose of hot caustic extraction (HCE) is to remove the short-chain hemicelluloses

(determined as S18, S10 fractions) for the production of reactive dissolving

pulps based on acid sulfite cooking. In contrast to cold caustic purification, which

relies on physical effects such as swelling and solubilization to remove short-chain

noncellulosic carbohydrates, hot alkali extraction utilizes primarily chemical reactions

on the entire pulp substrate for purification.

The treatment is carried out at low caustic concentration, typically 3–18 g L–1

NaOH, with pulp consistencies of 10–15% at temperatures ranging from 70 °C to

120 °C (occasionally 140 °c). As mentioned previously, hce is carried out solely

for sulfite pulps, because the same carbohydrate degradation reactions are

Involved in alkaline cooks (kraft, soda), at less severe conditions and thus avoiding

alkaline hydrolysis reactions. Therefore, HCE does not contribute much to the

purity of pulps derived from alkaline cooking processes. From the chemistry point

of view, HCE should be placed before any oxidative bleaching stage, as the efficiency

of purification is impaired as soon as aldehyde groups are oxidized to carboxyl

groups. It has been found that the gain in alpha-cellulose is related to the

copper number (or carbonyl content) of the unpurified pulp [30]. Consequently, if

measures are undertaken to stabilize the carbohydrates against alkaline degradation

either by oxidation (HClO2) or reduction (sodium borohydride), virtually no

purification is achieved [31,32]. However, for the production of low-grade dissolving

pulps with a focus on viscose applications, hot caustic extraction (E) and oxygen

delignification (O) are often combined into one single stage (EO) to reduce

costs. The reduction in purification efficiency is negligible, provided that the

degree of purification is limited to R18 values well below 94–95%.

952 8 Pulp Purification

8.4.1

Influence of Reaction Conditions on Pulp Quality and Pulp Yield

8.4.1.1 NaOHCharge and Temperature in E, (EO), and (E/O) Treatments

The NaOH charge is the most important parameter controlling the degree of purification

during HCE. At a given alkali dosage, the consistency determines the

alkali concentration in the purifying lye. According to Leugering [30], the gain in

alpha-cellulose is accelerated with increasing consistency at a given alkali charge,

as shown in Fig. 8.15.

0 1 2 3 4

90

91

92

93

94

95

5% consistency 10% consistency

Alpha-Cellulose [%]

Time [h]

Fig. 8.15 Alpha-cellulose versus time, calculated according to

the empiric formula developed by Leugering [30], with the following

assumptions: Initial alpha-cellulose content 90%, 4%

NaOH charge, 90 °C.

The relationship between the gain in alpha-cellulose content (Da) and NaOH

concentration multiplied by retention time has been derived on the basis of

spruce acid sulfite pulps:

Da _ __3_3 _ 0_1 _ con_ _ 0_13 _ _T _ 80__ _ _NaOHch _ con

100 _ con _ t__ 1

2_0_2 con_ _1_

where: con = consistency (%; validity range 5–15%); T = temperature ( °C; validity

range 80–97 °C);NaOHch= NaOHcharge (kg odt–1; validity range 34–228 kg odt–1);

and t = time (h; validity range 0–4 h).