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In the cooking process or, alternatively, white liquor can be used for the cold

extraction process. Another means of employing the excess lye is to use it for hot

alkaline purification, with the prerequisite that the production of hot alkali-purified

pulp considerably exceeds that of cold alkali-purified pulp. Recirculation of

the lye (after pressing) significantly deteriorates the result of the purification, due

to an accumulation of impurities derived from short-chain carbohydrate degradation

products, being characterized as beta- and gamma-celluloses. Beta-cellulose

Is defined as the precipitate formed upon acidification of an aqueous alkaline solution

containing the dissolved pulp constituents, while gamma-cellulose comprises

the carbohydrate residue in solution. The former consists of higher molecular-

weight, the latter of lower molecular-weight material.

These compounds can be (partly) removed by means of dialysis of (part of) the

press-lye [4,5]. In addition, inter- and even intramicellar swelling of pulps under

the conditions of cold caustic extraction (low temperature combined with high

alkali concentration in the vicinity of the swelling maximum) impedes the

removal of excess lye during the course of subsequent washing. An optimum between

purification performance and limitation of fiber swelling can be found by

adjusting the temperature and caustic charge.

The treatment of pulp with aqueous sodium hydroxide solution still represents

the principal means of producing highly purified dissolving pulp. When applying

these caustic treatments, the extent of purification can be controlled by adjusting

the appropriate conditions. The relationship between the process conditions, involving

both sodium hydroxide concentration and temperature, and the course of

934 8 Pulp Purification

reaction comprising the carbohydrate constituents of a selected hardwood sulfite

dissolving pulp is described in the next section.

8.2

Reactions between Pulp Constituents and Aqueous Sodium Hydroxide Solution

Wood pulp obtained by the acid sulfite process still contains considerable amounts

of low molecular-weight carbohydrates (hemicelluloses). These make the pulp less

suitable for many purposes as known for the production of cellulose acetate, highpurity

cellulose ethers or high-tenacity regenerated fibers. As mentioned previously,

the pulp is refined with alkali either at temperatures below 50 °C whereby

strong solutions of sodium hydroxide are used (characterized as cold caustic

extraction, CCE), or at higher temperatures using weaker alkaline solutions (characterized

as hot caustic extraction, HCE). In some cases, both processes are

applied subsequently (in any order: CCE before or after HCE) to obtain the highest

purity dissolving pulp derived from the sulfite cooking process. It is well

known that the extraction of wood pulp with strong sodium hydroxide solutions at

low temperatures produces higher levels of alpha-cellulose than with dilute solutions

at high temperatures, while the yields obtained are considerably higher. The

basis of both purification processes was developed during the 1940s and 1950s.

Hempel studied the solubility of viscose pulps at 20 °C in the range of NaOH concentration

between 1 and 20%, with the emphasis on maximum solubility [6].

Shogenji and associates treated chlorinated sulfite pulp at 25 °C with 3 to 12%

NaOH and investigated the alkaline solutions after treatment for total and combined

alkali [7]. Wilson and coworkers tested the alkali solubility of pulp in relation

to the alpha-cellulose determination, and stated that wood originally contains

appreciable amounts of gamma-cellulose of low degree of polymerization (10–30),

but no beta-cellulose [8]. The latter is formed during the pulping processes from

alpha-cellulose. Many studies have been conducted to determine phase-transition

during the treatment of pulp or cotton linters with alkaline solutions of varying

concentrations, using X-ray diffraction. Ranby studied the appearance of cellulose

hydrate when treating different cellulose substrates at 0 °C with increasing concentrations

of sodium hydroxide [9]. With cotton, the first indication of hydrate

cellulose occurs at 8% NaOH, whereas with wood pulp it occurs already at 6%

NaOH. The NaOH concentration necessary for transition is related to the water

sorption of the original cellulose, which means that cellulose undergoing transition

at low NaOH concentration has a high water sorption. An electron-microscopic

study of spruce holocellulose indicated that alpha-cellulose is built up of

micelle strings about 8 nm wide, whereas gamma-cellulose contains no strings

[10]. The beta-cellulose fraction appears to be a mixture of short string fragments

and small particles. An X-ray investigation showed that both alpha- and beta-celluloses

show the same type of lattice (cellulose II). The gamma-cellulose seems to

consist of several phases different from cellulose II. The beta-cellulose is assumed