Sulfite and Soda Pulping

Sulfite and Soda pulping
Types of Chemical Pulping
Sulfate(Kraft) Sulfite Soda
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Sulfite Pulping
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Introduction:
• The sulfite process produces wood pulp which is almost
pure cellulose fibers by using various salts of sulfurous acid to
extract the lignin from wood chips in large pressure vessels
called digesters.
• The salts used in the pulping process are either sulfites (SO32−),
or bisulfites (HSO3−), depending on the pH. The
counter ion can
be sodium (Na+), calcium (Ca2+), potassium (K+), magnesium (
Mg2+) or ammonium(NH4+).
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Processes involved in sulfite pulping
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1. Pulping liquor preparation
• The pulping liquor for most sulfite mills is made by burning sulfur with the correct
amount of oxygen to give sulfur dioxide, which is then absorbed into water to give
sulfurous acid.
S + O2 → SO2
SO2 + H2O ⇌ H2SO3
• Care must be taken to avoid the formation of sulfur trioxide since it gives
undesired sulfuric acid when it is dissolved in water.
2 SO2 + O2 → 2SO3
SO3 + H2O ⇌ H2SO4
• Sulfuric acid is undesirable since it promotes hydrolysis of cellulose without

contributing to delignification. 7
Pulping liquor preparation(contd..)
• The cooking liquor is prepared by adding the counter ions as hydroxides or
carbonates. For monovalent (Na+, K+ and NH4+) hydroxides, MOH:
H2SO3 + MOH → MHSO3 + H2O
MHSO3 + MOH → M2SO3 + H2O
• For divalent (Ca2+, Mg2+) carbonates, MCO3:
MCO3 + 2H2SO3 → M(HSO3)2 + CO2 + H2O

M(HSO3)2 + MCO3 → 2 MSO3 + CO2 + H2O
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2. Pulping
• Sulfite pulping is carried out between pH 1.5 and 2.5, depending on the
counterion to sulfite (bisulfite) and the ratio of base to sulfurous acid.
The pulp is in contact with the pulping chemicals for 4 to 14 hours and
at temperatures ranging from 130 to 160 °C, again depending on the
chemicals used.
• The electrophilic carbocations react with bisulfite ions (HSO3−)to give
sulfonates.
R-O-R' + H+ → R+ + R’OH
R+ + HSO3− → R-SO3H
• The sulfite process does not degrade lignin to the same extent that
the kraft process does and the lignosulfonates from the sulfite process
are useful byproducts. 9
3.Chemical Recovery
• The spent cooking liquor from sulfite pulping is usually called brown liquor, but
the terms red liquor, thick liquor and sulfite liquor are also used (compared
to black liquor in the kraft process).
• Pulp washers, using countercurrent flow, remove the spent cooking chemicals and
degraded lignin and hemicellulose.
• The extracted brown liquor is concentrated, in multiple effect evaporators. The
concentrated brown liquor can be burned in the recovery boiler to generate
steam and recover the inorganic chemicals for reuse in the pulping process or it
can be neutralized to recover the useful byproducts of pulping.
• The sulfite process can use calcium, ammonium, magnesium or sodium as a base.
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Byproducts
Sulfite pulping is generally less destructive than kraft pulping, so there are more
usable byproducts.
• Lignosulfonates
Chief among sulfite process byproducts are lignosulfonates, which find a wide
variety of uses. Lignosulfonates are used in tanning leather, making concrete,
drilling mud, drywall and so on.
Oxidation of lignosulfonates was used to produce vanillin (artificial vanilla).
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Other byproducts
Acid hydrolysis of hemicelluloses during sulfite pulping produces:
• monosaccharides
• predominantly mannose for softwoods
• xylose for hardwoods, which can be fermented to produce ethanol.
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Applications
• Commodity
Sulfite pulp remains an important commodity, especially for specialty papers and
as a source of cellulose for non-paper applications. It is used to make fine paper,
tissue, glassine and to add strength to newsprint.
• Dissolving pulp
A special grade of bleached sulfite pulp is known as dissolving pulp which is the
raw material for a wide variety of cellulose derivatives, for example rayon,
cellophane, cellulose acetate and methylcellulose.
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Soda Pulping
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Introduction:
• Soda pulping is a chemical process for making wood pulp with
sodium hydroxide as the cooking chemical.
• In the Soda-AQ process, anthraquinone (AQ) may be used as a pulping

additive to decrease the carbohydrate degradation.
• The soda process gives pulp with lower tear strength than other chemical
pulping processes (sulfite process and kraft process), but has still limited
use for easy pulped materials like straw and some hardwoods.
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Advantages of soda pulping over sulfite pulping
Delignification of rice straw by soda cooking is more rapid than that of wheat straw.
Corresponding with delignification, the brightness of the former is higher than that of
the latter.
The ash fraction is dissolved during soda cooking, although a few % of ash is still
contained in soda pulp. However, the ash fraction during alkaline sulfite pulping is
difficult to be dissolved, and 16 - 17% of ash are contained in pulp. Such a high amount
of ash may regulate the extensive application of alkaline sulfite pulp.
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Sulfite and Soda Pulping

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Sulfite and Soda pulping

Types of Chemical Pulping

Sulfate(Kraft) Sulfite Soda

• Sulfuric acid is undesirable since it promotes hydrolysis of cellulose without

• For divalent (Ca2+, Mg2+) carbonates, MCO3:

MCO3 + 2H2SO3 → M(HSO3)2 + CO2 + H2O

• In the Soda-AQ process, anthraquinone (AQ) may be used as a pulping

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