Sulphite Pulping

A Philadelphia chemist, Benjamin Tilghmnn, discovered that wood

could be softened and defibered with sulphurous acid (H 2S03).
However, he noted that sulphurous acid acting alone produced a
"burnt" or discolored pulp. He further discovered that the presence of
a cationic base such as calcium prevented the discoloration.

Definition:
The definitions for sulphite acid strengths and chemical applications
revolve around the fact that one molecule of calcium bisulphite is
chemically equivalent to one molecule each of sulphurous acid
(referred to as "free S02") and calcium sulphite
("combined S02"):

Hypothetical sulphite cooking analysis for three samples (g/100 ml)

Analysis of sulphite liquor;

 Measure out, in an inert atmosphere, 250± 1 ml of sample (V3).
 Add 2.0 ± 0.2 ml of hydrochloric acid (If the samples contain more
than 20 milliequivalents per litre of alkali, add extra hydrochloric
acid to bring the sample to neutrality or slight acidity and then the 2
ml excess.), followed by 50.00 ± 0.01 ml of M/240 potassium
iodate-iodine mixture. Mix by gentle swirling (If there is no free
iodine left after mixing, add further 50 ml portions of iodate-iodine
until the brown colour of free iodine is obtained. Note how much is
needed (V1).
 Titrate the excess iodine formed with M/40 sodium thiosulphate
solution. When the brown iodine colour becomes amber, add a few
 drops of starch indicator solution and continue titration until the
resultant blue colour disappears completely (The blue colour may
return on standing in air. This should be ignored as it is due to
oxidation of iodide by air). Note the volume of thiosulphate solution
used (V2).
 Using 250 ± 1 ml of water carry out steps as above and note the
volume of thiosulphate required (V4) for 50.00 ± 0.05 ml of the
M/240 iodate-iodine.

KIO3 + 5KI +6H2O 3H2O + 6KOH +3I2

Ca(HSO3)2 +I2 +2H2O H2SO4 +2H2O +CaI

2Na2S2O3 + I2 Na2S4O6 + 2NaI

Use of bases
(1) Calcium: Calcium  is the traditional base used in sulphite
pulping. Limestone (CaCO3) reacts with H2SO3 in pressurized
towers to produce the pulping liquor. The liquor is used at a pH
of 1–2 (maintained with excess SO 2) and cooking temperature
is 140°C. The traditional calcium acid sulphite cook must be
carried out at a low pH of about 1.5 because of the relative
insolubility of calcium. A higher pH would cause scaling
compounds to precipitate during cooking, leading to a
condition known as "liming up" of the digester.

Formation of sulphurous acid

Formation of Calcium bisulphite

Intermediate reactions

or [Combined S02] + [Free S02]~[Bisulphite]

(2) Magnesium: Magnesium-based sulphite pulping is carried
out at a pH below 5 and is characterized relative to the
other bases by intermediate pulping rate, moderate
scaling and screenings, and relatively simple chemical
recovery. 
The recovery process used in magnesium-based sulphite
pulping the "Magnefite" process is well developed. The
concentrated brown liquor is burned in a recovery boiler,
producing magnesium oxide and sulfur dioxide, both of
which are recovered from the flue gases. Magnesium oxide
is recovered in a wet scrubber to give
a slurry of magnesium hydroxide.

MgO + H2O → Mg(OH)2

This magnesium hydroxide slurry is then used in another
scrubber to absorb sulphur dioxide from the flue
gases producing a magnesium bisulphite solution that is
clarified, filtered and used as the pulping liquor.

Mg(OH)2 + 2 SO2 → Mg(HSO3)2

(3) Sodium: Sodium-based sulphite pulping can be carried out
at any pH. NaOH or Na2CO3 may be used to form the
cooking liquor from H2SO3. The process is characterized by
a slow pulping rate, low amounts of screenings, and low
scaling and complex chemical recovery.

(4) Ammonium: Ammonium-based sulphite pulping is very

similar to sodium-based pulping (because the ammonium
ion is very similar to the sodium ion), except for two
important differences. The cooking rate is faster than the
other three bases mentioned, and the ammonium ion is
lost in chemical recovery by combustion; however, the use
of fresh ammonia (which reacts as ammonium hydroxide)
allows the sulfur to be recovered in a relatively simple
process. The upper practical pH limit is about 9; above this
pH, free ammonia begins to be significant.
NH3 +H2O NH4OH
NH4OH + H2SO3 (NH4)HSO3 +H2O
 Conditions for sulphite cooking process

Reactions:
1. Free sulphurous acid combines with lignin to produce
relatively insoluble lignosulphonic acid.
2. In the presence of the base, lignosulfonic salts are
formed which are more soluble.
3. The sulphonated lignin undergoes cleavage into smaller
and more soluble molecular fragments due to hydrolysis
reactions.
4. Hemicelluloses are hydrolyzed into soluble sugars.
5. Cellulose is relatively stable to chemical attack by the
sulphite liquor.
6. Easier delignification (compared to the kraft
process) makes the sulphite process well suited to
produce pulps rich in hemicelluloses, which are ideal
for making such paper grades as greaseproof and
glassine.
7. At the same time, the ease of hemicellulose
removal on prolonged sulphite cooking (using
somewhat higher temperature and acidity) also
makes possible the production of pulp with high
cellulose purity, suitable for dissolving grades and
special opaque papers.
8. The poly condensation of lignin is a highly
undesirable reaction which can occur under
conditions of high acid concentration and/or high
temperature.
9. The dark-colored and insoluble compounds that are
formed give rise to "burnt" cook.
10. Polycondensation of lignin always occurs when sulphurous
acid is used alone as a pulping agent. In the presence of a
base, the system is buffered and polycondensation is
usually prevented.
11. Polycondensation reactions are much less likely to
occur with the monovalent bases, sodium and
ammonium, especially in the pH range of acid
bisulphite and bisulphite cooking. Because of more
rapid penetration and lower acid concentrations,
faster come-up times and higher temperatures can be
used, so that total cooking time can be significantly
reduced in comparison to calcium acid sulphite cooks

Variables affecting sulphite cooking:

Suggested studies:

Questions answers: https://www.sanfoundry.com/pulp-paper-assessment-questions-

answers/

Analysis of sulphite liquor:

http://standingcommitteeofanalysts.co.uk/Archive/Determination_of_sulphite_sulphur_dioxide_thi
osulphate_and_thiocyanate_with_notes_on_the_determination_of_total_sulphur_and_other_sulph
ur_comp.pdf