
- •Pulp Purification Herbert Sixta
- •9.2.2.1 Introduction
- •Introduction
- •10.4 Emissions to the Aquatic Environment
- •Is converted into carbon dioxide, while the other half is converted into biomass
- •Into alcohols and aldehydes; (c) conversion of these intermediates into acetic acid and
- •10 Environmental Aspects of Pulp Production
- •In North America, effluent color is a parameter which must be monitored.
- •It is not contaminated with other trace elements such as mercury, lead, or cadmium.
- •10.6 Outlook
- •Increase pollution by causing a higher demand for a chemical to achieve identical
- •In addition negatively affect fiber strength, which in turn triggers a higher
- •Introduction
- •2002, Paper-grade pulp accounts for almost 98% of the total wood pulp production
- •Important pulping method until the 1930s) continuously loses ground and finds
- •Importance in newsprint has been declining in recent years with the increasing
- •Isbn: 3-527-30999-3
- •Virtually all paper and paperboard grades in order to improve strength properties.
- •In fact, the word kraft is the Swedish and German word for strength. Unbleached
- •Importance is in the printing and writing grades. In these grades, softwood
- •In this chapter, the main emphasis is placed on a comprehensive discussion of
- •1010 11 Pulp Properties and Applications
- •Is particularly sensitive to alkaline cleavage. The decrease in uronic acid content
- •Xylan in the surface layers of kraft pulps as compared to sulfite pulps has been
- •80% Cellulose content the fiber strength greatly diminishes [14]. This may be due
- •Viscoelastic and capable of absorbing more energy under mechanical stress. The
- •11.2 Paper-Grade Pulp 1011
- •Various pulping treatments using black spruce with low fibril
- •In the viscoelastic regions. Fibers of high modulus and elasticity tend to peel their
- •1012 11 Pulp Properties and Applications
- •11.2 Paper-Grade Pulp
- •Viscosity mL g–1 793 635 833 802 1020 868 1123
- •Xylose % od pulp 7.3 6.9 18.4 25.5 4.1 2.7 12.2
- •11 Pulp Properties and Applications
- •Inorganic Compounds
- •11.2 Paper-Grade Pulp
- •Insight into many aspects of pulp origin and properties, including the type of
- •Indicate oxidative damage of carbohydrates).
- •In general, the r-values of paper pulps are typically at higher levels as predicted
- •Is true for sulfite pulps. Even though the r-values of sulfite pulps are generally
- •Is rather unstable in acid sulfite pulping, and this results in a low (hemicellulose)
- •11 Pulp Properties and Applications
- •Ing process, for example the kraft process, the cellulose:hemicellulose ratio is
- •Increases by up to 100%. In contrast to fiber strength, the sheet strength is highly
- •Identified as the major influencing parameter of sheet strength properties. It has
- •In contrast to dissolving pulp specification, the standard characterization of
- •Is observed for beech kraft pulp, which seems to correlate with the enhanced
- •11.2 Paper-Grade Pulp
- •11 Pulp Properties and Applications
- •Is significantly higher for the sulfite as compared to the kraft pulps, and indicates
- •11.2 Paper-Grade Pulp
- •Xylan [24].
- •11 Pulp Properties and Applications
- •11.2 Paper-Grade Pulp
- •11 Pulp Properties and Applications
- •Introduction
- •Various cellulose-derived products such as regenerated fibers or films (e.G.,
- •Viscose, Lyocell), cellulose esters (acetates, propionates, butyrates, nitrates) and
- •In pulping and bleaching operations are required in order to obtain a highquality
- •Important pioneer of cellulose chemistry and technology, by the statement that
- •11.3 Dissolving Grade Pulp
- •Involves the extensive characterization of the cellulose structure at three different
- •Is an important characteristic of dissolving pulps. Finally, the qualitative and
- •Inorganic compounds
- •11 Pulp Properties and Applications
- •11.3.2.1 Pulp Origin, Pulp Consumers
- •Include the recently evaluated Formacell procedure [7], as well as the prehydrolysis-
- •11.3 Dissolving Grade Pulp
- •Viscose
- •11 Pulp Properties and Applications
- •11.3.2.2 Chemical Properties
- •11.3.2.2.1 Chemical Composition
- •In the polymer. The available purification processes – particularly the hot and cold
- •11.3 Dissolving Grade Pulp
- •In the steeping lye inhibits cellulose degradation during ageing due to the
- •Is governed by a low content of noncellulosic impurities, particularly pentosans,
- •Increase in the xylan content in the respective viscose fibers clearly support the
- •11.3 Dissolving Grade Pulp
- •Instability. Diacetate color is measured by determining the yellowness coefficient
- •Xylan content [%]
- •11 Pulp Properties and Applications
- •Xylan content [%]
- •11.3 Dissolving Grade Pulp
- •11.3 Dissolving Grade Pulp
- •Is, however, not the only factor determining the optical properties of cellulosic
- •In the case of alkaline derivatization procedures (e.G., viscose, ethers). In industrial
- •11.3 Dissolving Grade Pulp
- •Viscose
- •Viscose
- •In order to bring out the effect of mwd on the strength properties of viscose
- •Imitating the regular production of rayon fibers. To obtain a representative view
- •11 Pulp Properties and Applications
- •Viscose Ether (hv) Viscose Acetate Acetate
- •Xylan % 3.6 3.1 1.5 0.9 0.2
- •1.3 Dtex regular viscose fibers in the conditioned
- •11.3 Dissolving Grade Pulp
- •Is more pronounced for sulfite than for phk pulps. Surprisingly, a clear correlation
- •Viscose fibers in the conditioned state related to the carbonyl
- •1038 11 Pulp Properties and Applications
- •In a comprehensive study, the effect of placing ozonation before (z-p) and after
- •Increased from 22.9 to 38.4 lmol g–1 in the case of a pz-sequence, whereas
- •22.3 To 24.2 lmol g–1. The courses of viscosity and carboxyl group contents were
- •Viscosity measurement additionally induces depolymerization due to strong
- •11 Pulp Properties and Applications
- •Increasing ozone charges. For more detailed
- •11.3 Dissolving Grade Pulp
- •Is more selective when ozonation represents the final stage according to an
- •11.3.2.3 Supramolecular Structure
- •1042 11 Pulp Properties and Applications
- •Is further altered by subsequent bleaching and purification processes. This
- •Involved in intra- and intermolecular hydrogen bonds. The softened state favors
- •11.3 Dissolving Grade Pulp
- •Interestingly, the resistance to mercerization, which refers to the concentration of
- •11 Pulp Properties and Applications
- •Illustrate that the difference in lye concentration between the two types of dissolving
- •Intensity (see Fig. 11.18: hw-phk high p-factor) clearly changes the supramolecular
- •11.3 Dissolving Grade Pulp
- •Viscose filterability, thus indicating an improved reactivity.
- •11 Pulp Properties and Applications
- •Impairs the accessibility of the acetylation agent. When subjecting a low-grade dissolving
- •Identification of the cell wall layers is possible by the preferred orientation of
- •Viscose pulp (low p-factor) (Fig. 11.21b, top). Apparently, the type of pulp – as well
- •11 Pulp Properties and Applications
- •150 °C for 2 h, more than 70% of a xylan, which was added to the cooking liquor
- •20% In the case of alkali concentrations up to 50 g l–1 [67]. Xylan redeposition has
- •11.3 Dissolving Grade Pulp
- •Xylan added linters cooked without xylan linters cooked with xylan
- •Viscosity
- •In the surface layer than in the inner fiber wall. This is in agreement with
- •11 Pulp Properties and Applications
- •Xylan content in peelings [wt%]
- •Xylan content located in the outermost layers of the beech phk fibers suggests
- •11.3.2.5 Fiber Morphology
- •11 Pulp Properties and Applications
- •50 And 90%. Moreover, bleachability of the screened pulps from which the wood
- •11.3.2.6 Pore Structure, Accessibility
- •11.3 Dissolving Grade Pulp
- •Volume (Vp), wrv and specific pore surface (Op) were seen between acid sulfite
- •11 Pulp Properties and Applications
- •Irreversible loss of fiber swelling occurs; indeed, Maloney and Paulapuro reported
- •In microcrystalline areas as the main reason for hornification [85]. The effect of
- •105 °C, thermal degradation proceeds in parallel with hornification, as shown in
- •Increased, particularly at temperatures above 105 °c. The increase in carbonyl
- •In pore volume is clearly illustrated in Fig. 11.28.
- •11.3 Dissolving Grade Pulp
- •Viscosity
- •11 Pulp Properties and Applications
- •Increase in the yellowness coefficient, haze, and the amount of undissolved particles.
- •11.3.2.7 Degradation of Dissolving Pulps
- •In mwd. A comprehensive description of all relevant cellulose degradation processes
- •Is reviewed in Ref. [4]. The different modes of cellulose degradation comprise
- •11.3 Dissolving Grade Pulp
- •50 °C, is illustrated graphically in Fig. 11.29.
- •11 Pulp Properties and Applications
- •In the crystalline regions.
- •11.3 Dissolving Grade Pulp
- •Important dissolving pulps, derived from hardwood, softwood and cotton linters
- •11.3 Dissolving Grade Pulp 1061
- •Xylan rel% ax/ec-pad 2.5 3.5 1.3 1.0 3.2 0.4
- •Viscosity mL g–1 scan-cm 15:99 500 450 820 730 1500 2000
- •1062 11 Pulp Properties and Applications
11.3 Dissolving Grade Pulp
Additional post cleaning by means of a centricleaner further reduced the
amount of resins, thus improving viscose filterability. The particle spectrum in
the viscose demonstrates both a clear reduction in the particle volume and a shift
of the average particle size to lower values (Fig. 11.10).
The results confirm that reinforced oxidation, for example by ozone, contributes
to an improved dispersibility of pulp resins, and this is an important prerequisite
for the effective separation of these impurities. The efficiency of resin removal
can be further enhanced by additional post-cleaning operations.
Although a certain amount of pulp resin may be beneficial for subsequent processing
steps, by improving accessibility to the cellulose substrate, practical experience
has taught that the best way to control extractives is to take measures to keep
them at a low level [32]. When the resin content falls below a certain level, the
homogeneity of subsequent reactions may be impaired because of a lowered surface
activity. In this case, the addition of small amounts of synthetic surface active
agents overcomes that deficiency.
Residual lignin, brightness
The residual lignin content in dissolving pulps is generally very low. The kappa
number, which specifies the amount of oxidizable (by KMnO4) structures containing
double bonds in the pulp, is typically between 0.2 and 0.5 units which translates
to a residual lignin content of about 0.05% [33]. The main reason for aiming
at a low kappa number is the high demand on optical properties. Residual lignin
structures strongly contribute to yellowing of the cellulosic products. The highest
demands on brightness and brightness stability are given for viscose, lyocell, and
acetate pulps. Similar brightness levels are required for dissolving pulps converted
to cellulose ethers for application in foodstuff and pharmaceuticals. Residual lignin
Is, however, not the only factor determining the optical properties of cellulosic
substances. Therefore, the relationship between pulp brightness and brightness
of the final product is also dependent upon the processing conditions, especially
In the case of alkaline derivatization procedures (e.G., viscose, ethers). In industrial
operations using constant conditions, pulp brightness is clearly reflected in
the brightness of the final product.
Brightness – and thus residual lignin – is not a concern for pulps used for technical-
grade cellulose ethers (major applications: textile, paper, drilling muds, ceramics,
etc.). Nevertheless, bleaching to brightness levels of about 70–75% ISO is
necessary to improve pulp reactivity and prevent precipitation of lignin compounds
in subsequent processing steps.
The residual lignin is not only a concern for optical properties, but also governs
the processability of dissolving pulps. It is reported that viscose filterability (determined
by the clogging constant) gradually deteriorates when increasing the residual
lignin content from about 0.17 to 0.36% [34].
Inorganic Compounds
The presence of certain inorganic compounds such as silicates, Ca salts, and catalytically
active transition metal ions (Fe, Mn, Co, etc.) clearly impairs the filterabil-
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11 Pulp Properties and Applications
ity and spinnability of a cellulose spinning dope (e.g., viscose or lyocell type of
fibers). Moreover, pulp contamination with inorganic compounds leads to a gradual
clogging of the spinnerets, and this alters the uniformity of the fiber titer [13].
In particular, the cations Ca2+ and Fe2+, as well as silicates, are considered to be
detrimental in this respect. Although Fe(II), and to a lesser extent Cu(II), promote
light-induced yellowing, both cations are involved in detrimental degradation reactions
in the presence of hydrogen peroxide bleaching (Fenton-type reaction).
Thus, all necessary measures must be undertaken (acid wash, chelation stage,
etc.) to remove catalytically active cations.
Surprisingly, most of the harmful ash components are not distributed homogeneously
in the pulp, but are present as particulates in certain cell fractions, particularly
in the parenchyma cells [35]. Therefore, the only promising way to reduce
the amount of harmful ash components is an efficient mechanical pulp treatment
which applies combined pressure screening of unbleached pulp and centrifugal
cleaning after bleaching. This treatment ensures the removal of extremely small
debris such as sand, bark specks, and shives. Again, the best way to control inorganic
compounds is to reduce them to the lowest level economically feasible.
11.3.2.2.2 Macromolecular Properties
Molar mass, molar mass distribution
Since celluloses from natural sources and after chemical treatment are always
polydisperse, the determination of the average molecular weight (e.g., by viscosimetry)
is insufficient to predict specific product properties. Additional information
is provided by the measuring molecular weight distribution (MWD) of dissolving
pulps.
Measurements of MWD reveal a multimodal distribution for pulps produced
according to acid sulfite cooking, while the PHK pulps show a rather uniform
MWD. Dissolving pulps, being representative of various applications including
viscose, acetate and high-viscosity ether, are compared in Fig. 11.11.
The numerical evaluation of the MWD, as well as additional pulp quality parameters,
are included in Tab. 11.7. As expected, the sulfite dissolving pulps (viscose,
high-viscosity ether) reveal a rather broad MWD, as indicated by the high PDI.
This is also reflected in the higher amount of short-chain molecules (DP <100),
lower values for the alkali resistances, and the large difference between R18 and
R10 when comparing at a similar viscosity level. In the case of a high-viscosity
ether pulp, the comparison is not valid because the entire molecular weight is
shifted to higher values (Tab. 11.7).
There are many reports which confirm that the chain-length distribution in the
dissolving pulp is a crucial property in the production of rayon fibers [37]. The
short-chain molecules represent the weakest part in the fiber: the shorter the molecules,
the lower will be the number of molecules linking the crystalline regions.
Avela et al. were able to show that all strength characteristics are significantly
reduced with an increase in the low molecular-weight fraction [38]. Treiber
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