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As mentioned earlier (see Section 4.3.2), the extent of delignification is dependent
upon the ionic product, [H+]·[HSO3
– ], whereas carbohydrate degradation is largely
controlled by the acidity of the cooking liquor, [H+]. The ratio of delignification to
carbohydrate removal during the sulfite cook, as given in Eq. (179):
delignification
carbohydrate degradation _
k ′ _ H _ _ HSO _3 k __ H _
k ′
k _ HSO _3 _179_
is therefore related to the hydrogen sulfite ion concentration. Consequently, the
ratio of delignification to carbohydrate hydrolysis velocities during the sulfite cook
increases with the growing buffer capacity of the cooking liquor. Moreover, both
lignin and carbohydrate degradation reactions are controlled by temperature and
time. Although the activation energies for delignification and carbohydrate
removal are somewhat contradictory, it is agreed that the temperature-dependence
of the carbohydrate degradation velocity is greater than that of the delignification
rate [4,8]. This explains why the hemicellulose content in a sulfite pulp increases
4.3 Sulfite Chemical Pulping 437
with decreasing cooking temperature at a given kappa number. With progressive
sulfite cooking, the ratio between the hydrogen ion and hydrogen sulfite ion concentrations
increases, which consequently accelerates the hemicellulose degradation.
This comparative ease of hemicellulose removal on prolonged sulfite cooking
makes it possible to produce dissolving pulps of high cellulose purity.
To follow the change in the composition of the wood components during magnesium
acid sulfite cooking of beech wood, extensive laboratory trials in the Hfactor
range from 0 to 250 have been conducted [14]. At given sulfite cooking conditions,
comprising total and free SO2 concentrations of 0.76 and 0.32 mol L–1,
respectively, a liquor-to-wood ratio of 2.4:1 and a cooking temperature of 148 °C,
the degradation pattern of the two main noncellulosic wood components – lignin
and xylan – differs significantly, as shown by the lignin-xylan ratio in Fig. 4.162.
After a short induction period, the degradation of lignin proceeds significantly
faster than xylan removal, up to an H-factor of approximately 130. When prolonging
the sulfite cook beyond an H-factor of 160, the xylan removal rate finally
increases significantly over the delignification rate, as shown in Tab. 4.58.
The other carbohydrate components of the hemicelluloses fractions hydrolyze
at different rates, depending on their chemical structure and accessibility. Furanosides
are known to hydrolyze more rapidly than pyranosides, which accounts for
the rapid dissolution of arabinose during sulfite cooking [15](T ab. 4.58). In good
agreement with the results from acid sulfite pulping, methyl-b-d-mannose is
cleaved about 5.7 times and both methyl-b-d-galactose and methyl-b-d-xylose
0 50 100 150 200 250
Lignin-to-Xylan conc. ratio
Yield [% on od wood]
H-Factor
Cellulose Lignin Xylan
Rare Sugars Total Yield
0,1
0,4
0,7
1,0
1,3
Lignin/Xylan ratio
Fig. 4.162 Course of the main wood components
in the solid phase during acid magnesium
sulfite cooking of beech wood [13]. Cooking
conditions comprise a total SO2 concentration
of 0.76 mol L–1, a free SO2 concentration of
0.32 mol L–1 free SO2, a liquor-to-wood ratio of
2.4:1, and a cooking temperature of 148 °C.
438 4 Chemical Pulping Processes
4.3 Sulfite Chemical Pulping 439
Tab. 4.58 Characterization of the (dissolving) pulp composition through acid magnesium sulfite cooking of beech wood
(according to [13]).
Label H-Factor Yield Lignin Kappa R10 R18 Viscosity COOH CO Copper# Lignin Glucan Xylan Arabinan Mannan Galactan DXyl/DLign
[% odw] [% odw] [mL g–1] [lmol
g–1]
[lmol
g–1]
[%] [% odw]
0 100 24.5 24.5 41.6 19.5 0.7 1.1 0.8
Mg 433 18 87.7 20.8 100.8 65.7 69.4 18.2 40.6 14.5 0.0 1.1 0.4 1.4
Mg 434 37 71.0 15.7 79.4 70.5 73.1 11.1 40.2 9.4 0.0 1.1 0.1 1.0
Mg 435 60 61.2 10.8 62.5 74.1 76.5 78.4 6.6 40.5 6.9 0.0 0.9 0.1 0.5
Mg 436 90 51.2 5.2 25.1 84.3 86.9 1096 103.4 51.7 1.8 2.7 40.5 5.1 0.0 0.8 0.0 0.3
Mg 437 130 47.9 1.5 9.2 85.9 88.5 1064 56.3 42.9 1.7 0.7 40.1 4.0 0.0 0.6 0.0 0.3
Mg 438 160 46.9 0.9 5.6 86.2 89.6 896 41.5 41.0 1.9 0.4 40.5 3.2 0.0 0.5 0.0 1.2
Mg 439 180 45.9 0.8 5.0 86.7 90.2 775 28.0 41.0 1.8 0.4 39.8 2.9 0.0 0.5 0.0 2.7
Mg 420 210 44.3 0.6 4.0 87.3 90.6 669 27.0 1.9 0.3 39.3 2.3 0.0 0.4 0.0 4.9
Mg 408 249 42.5 0.6 3.5 86.4 92.4 479 21.9 2.2 0.3 38.9 1.3 0.0 0.3 0.0 17.0
[16,19]CO = carbonyl content
0 50 100 150 200 250
Yield [%] / Viscosity*10 [ml/g]
Lignin Cellulose Xylan Arabinose
Mannose Galactose
Pulp Composition [%]
H-Factor
Yield Viscosity
Fig. 4.163 Course of the pulp yield and pulp
viscosity, as well as the main wood components,
in the solid phase during acid magnesium
sulfite cooking of beech wood [13].
Cooking conditions comprise a total SO2
concentration of 0.76 mol L–1, a free SO2 concentration
of 0.32 mol L–1 free SO2, a liquor-towood
ratio of 2.4:1, and a cooking temperature
of 148 °C.
about 9.1 times as fast as methyl-b-d-glucose [15]. Cellulose is, however, significantly
more resistant toward acid-catalyzed hydrolysis due to its partly crystalline
structure than those figures from model substrates imply. According to the material
balance shown in Tab. 4.58 and Fig. 4.163, almost no cellulose is removed
until very high H-factors are applied, as are necessary for the production of lowviscosity
dissolving pulps.
The comparative ease of degradation of glucan-containing hemicelluloses (e.g.,
glucomannan) indicates that the supramolecular structure of the carbohydrates
exerts a more important influence on the hydrolysis rate as compared to the conformational
structure of the polysaccharides. The presence of the 4- O -methyl-dglucuronic
acid side chain of the xylan is known to stabilize the glycosidic bonds
towards acid hydrolysis, and this explains the persistence of glucuronic groups
during sulfite cooking. Assuming that the content of carboxylic groups in pulp is
related to the glucuronic acid side chains of the xylan, it can be shown that the
content of the acid side chain is reduced along with the reduction in xylan content.
A closer examination of these results shows that the molar ratio xylan-to-carboxylic
acid groups is increased significantly, from about 7:1 to 17:1, by reducing
the xylan content of the pulp from 10% to 6%. This indicates that, at this stage of
sulfite cooking, the glucuronic acid side chains are cleaved from the pulp xylan
(Fig. 4.164). As the final stage of the cook is characteristic for dissolving pulp production,
the molar ratio xylan-to-carboxylic acid groups decreases again to a value
440 4 Chemical Pulping Processes
3 4 5 6 7 8 9 10
COOH content in pulp
Molar xylan-to-COOH ratio
COOH content [ìmol/g pulp]
Xylan content [% on pulp]
molar xylan-to-COOH ratio
Fig. 4.164 Carboxylic acid groups in relation to
the xylan content of beech dissolving pulps
produced by an acid magnesium sulfite process
[13]. Cooking conditions comprise a total
SO2 concentration of 0.76 mol L–1, a free SO2
concentration of 0.32 mol L–1 free SO2, a liquorto-
wood ratio of 2.4:1, and a cooking temperature
of 148 °C.
of about 11:1, and this can be explained by there being a preferred hydrolysis of
xylan with a low degree of substitution.
Carboxylic groups may, however, also be introduced as aldonic acid groups to
pulp constituents (e.g., hemicelluloses) by oxidative action of the hydrogen sulfite
ions. The conclusion is that the analysis of carboxylic groups alone does not provide
an unequivocally clear picture about the course of the glucuronic acid side
chain concentration during acid sulfite cooking.
Along with the progress of cooking, the molecular weight of the residual carbohydrate
fraction decreases. The cleavage of glycosidic bonds creates new reducing end
groups, and this accounts for the increase in carbonyl groups. However, the determination
of carbonyl content in the pulp by a new method using fluorescence labeling
(with carbazole-9-carboxylic acid; CCOA) [16–19]re veals a reduction in the carbonyl
content of pulps as sulfite cooking proceeds from H-factor 60 to about 160. This is
most likely due to a disproportionately high dissolution rate of short-chain polysaccharides
as compared to the degradation of the solid-phase polysaccharides (see
Tab. 4.58). At the very late stage of the sulfite cook, the carbonyl content increases (as
determined by the classical copper number method), despite the significant removal
of short-chain hemicelluloses. Clearly, additional carbonyl groups along the chains
are introduced by oxidative processes. The presence of carbonyl groups within the
anhydroglucose unit (AHG) is indirectly demonstrated by an increase in the (hot)
alkali solubility of these pulps, and to some extent also by a decreasing R10 content
[20]. Following both the residues after a treatment in 10%and 18% NaOHconcentration
(R10-, R18-contents, respectively) and the cellulose content of the pulp, it can be
seen that during the early stages of sulfite cooking (H-factor 20–100) much of the
4.3 Sulfite Chemical Pulping 441
0 50 100 150 200 250
R18 R10 Cellulose
Cellulose / R18 / R10 [%]
H-Factor
Fig. 4.165 Course of the alkali resistances, R18
and R10, in relation to the cellulose content of
beech dissolving pulps prepared by the magnesium
sulfite process [13]. Cooking conditions
comprise a total SO2 concentration of
0.76 mol L–1, a free SO2 concentration of
0.32 mol L–1 free SO2, a liquor-to-wood ratio of
2.4:1, and a cooking temperature of 148 °C.
noncellulosic material resists alkaline treatment, indicating a high molecular
weight of the hemicellulose fraction (Fig. 4.165).
As sulfite cooking proceeds, the gap between the cellulose content and the alkali
resistances diminishes. The cellulose content finally exceeds the R10 content of
the pulps being produced at H-factors greater than 180. Prolonged cooking leads
to a degradation of pulp cellulose, creating increasing fractions of alkali-soluble
cellulose. The course of the R18-content parallels the cellulose content, and both parameters
become equal after prolonged cooking (H-factor about 250). The good correspondence
between the cellulose and the R18 content in sulfite pulps has yet to be
confirmed in a detailed study on the quality evaluation of dissolving pulps [21].
Further information regarding the nature of the noncellulosic polysaccharide
fraction in the pulp is provided by quantitative characterization of the b– and
c-cellulose fractions. According to the results shown in Fig. 4.166, the removal of
c-cellulose appears to occur with an initial rapid phase, followed by a second
slower phase, while the b-cellulose content decreases almost linearly. The rapid
removal of the low molecular-weight hemicellulose fraction (c-cellulose) reflects
the high susceptibility of the short-chain amorphous wood polysaccharides
towards acid-catalyzed hydrolysis.
The molecular weight of the b-cellulose fraction decreases, whilst at the same
time the amount of b-cellulose diminishes. The reduction in molecular weight
decreases with increasing cooking intensity, and finally levels off at H-factors
higher than 180 (Fig. 4.167). The polydispersity of the b-fraction appears to
increase slightly when pulps are subjected to prolonged cooking.
442 4 Chemical Pulping Processes
0 50 100 150 200 250
gamma-cellulose beta-cellulose
Dissolved hemifraction [% od pulp]
H-factor
Fig. 4.166 Course of the b– and c-cellulose
contents of beech dissolving pulps prepared by
the magnesium sulfite process [13]. Cooking
conditions comprise a total SO2 concentration
of 0.76 mol L–1, a free SO2 concentration of
0.32 mol L–1 free SO2, a liquor-to-wood ratio of
2.4:1, and a cooking temperature of 148 °C.
3.0 3.5 4.0 4.5 5.0
0.0
0.1
0.2
H-Factor 230
11.8 / 7.1
H-Factor 180
11.8 / 8.6
H-Factor 130
12.9 / 10.3
H-Factor 60
15.3 / 12.4
H-Factor 18
21.8 / 17.3
weight fractions
Log Molar Mass
Fig. 4.167 Molecular weight distribution of isolated
b-cellulose fractions from beech dissolving
pulps prepared by the magnesium sulfite
process [13]. Numbers in figure represent MW
(left) and MN (right), both in [KDa]. Cooking
conditions comprise a total SO2 concentration
of 0.76 mol L–1, a free SO2 concentration of
0.32 mol L–1 free SO2, a liquor-to-wood ratio of
2.4:1, and a cooking temperature of 148 °C.
4.3 Sulfite Chemical Pulping 443
0 50 100 150 200 250
Pulp Alkalicellulose
Xylan content in residue [%]
H-Factor
Fig. 4.168 Course of the xylan content in pulp
and regenerated alkali-cellulose derived from
dissolving pulps prepared by the magnesium
sulfite process [13]. Cooking conditions
comprise a total SO2 concentration of
0.76 mol L–1, a free SO2 concentration of
0.32 mol L–1 free SO2, a liquor-to-wood ratio of
2.4:1, and a cooking temperature of 148 °C.
The high molecular-weight xylan fraction of the wood, which is characterized by
the proportion of xylan which is resistant to a treatment in 18 wt% NaOH at 50 °C
(steeping lye), is degraded within the first 60 min of sulfite cooking. As cooking
proceeds beyond an H-factor of 60, the alkali-resistant xylan content in the pulp
levels off and remains constant at approximately 0.8% on pulp (Fig. 4.168). As
this amount of xylan is even fiber-forming (and is present in regenerated fibers),
it can be assumed that this alkali-resistant xylan fraction is co-crystallized with cellulose
and is thus (almost) free of side chains.
The relationship between the amount of alkali-resistant xylan and the molecular
weight of the b-cellulose fraction reveals that a certain molecular weight must be
exceeded in order for xylan to be characterized as alkali-resistant. This observation
is in full agreement with the fiber-forming properties of alkali-resistant xylan
(Fig. 4.169).
The amount of carbohydrates dissolved does not correspond to the yield of neutral
sugars present in the sulfite spent liquor. Depending on both the composition
of the cooking liquor and the cooking intensity, the dissolved carbohydrates
undergo further degradation to monosaccharides (neutral sugars), aldonic acids,
furfural from pentoses, acetic acid, glucuronic acid and methanol from the cleavage
of the side chains and unspecified condensation products with reactive intermediates
from dehydration reactions of pentoses [22,23]. In the spent liquor of a
444 4 Chemical Pulping Processes
0.5 1.0 1.5 2.0 2.5 3.0
Weight-average MW of â-fraction [kDa]
Alkali-resistant xylan [% on pulp]
Fig. 4.169 Weight-average molecular weight of
the b-cellulose fraction as a function of the
amount of alkali-resistant xylan isolated from
beech dissolving pulps prepared by the magnesium
sulfite process [13]. Cooking conditions
comprise a total SO2 concentration of
0.76 mol L–1, a free SO2 concentration of
0.32 mol L–1 free SO2, a liquor-to-wood ratio of
2.4:1, and a cooking temperature of 148 °C.
beech paper-grade pulp comprising an H-factor of 90–130, approximately 25% of
the dissolved neutral sugars are still present as oligosaccharides (Tab. 4.59).
By further continuing the acid sulfite cook, the remaining oligosaccharides
quickly hydrolyze to the corresponding monosaccharides. Therefore, the spent
liquor of a typical dissolving cook contains only monosaccharides as neutral
sugars (Tab. 4.59). The predominant monosaccharide present in the spent liquor
of hardwood cooks (e.g., beech wood) is xylose, as would be expected from the carbohydrate
composition of beech wood (see Tab. 4.42). The xylose yield – and also
the total amount of dissolved carbohydrate-derived materials – reaches a maximum
at an H-factor of 160, which corresponds to a medium- to high-viscosity dissolving
pulp (Fig. 4.170).
The decrease in pentose (xylose and arabinose) concentration during the late
stages of the cook indicates both the increase in furfural formation and, in addition,
the occurrence of acid-catalyzed decomposition reactions to undefined condensation
products. The data in Tab. 4.59 confirm the increase in furfural concentration
in the spent liquor, but this does not account for the entire amount of xylan
removed from the pulp. In contrast to the pentoses, the concentration of hexoses
increases slightly as cooking proceeds beyond H-factors of 160. Glucose contributes
the highest concentration increase, thus indicating a progressive cellulose
degradation in the case of low-viscosity dissolving pulp production. During the
early stages of a sulfite cook, aldoses are already oxidized to aldonic acids, with
hydrogen sulfite ions serving as the oxidizing agent. In the final cooking phase,
4.3 Sulfite Chemical Pulping 445
446 4 Chemical Pulping Processes
Tab. 4.59 Characterization of the dissolved wood components and their degradation products in the course of acid magnesium
sulfite cooking of beech wood (according to [13]).
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