Definition of SULFITE LIQUOR

1. : the bisulfite solution used in making pulp by the sulfite process

Bisulfite ion (IUPAC-recommended nomenclature: hydrogen sulfite) is the ion HSO3. Salts
containing the HSO3 ion are termed bisulfites also known as sulfite lyes. For example, sodium
bisulfite is NaHSO3.

Reactions

Bisulfite salts are typically prepared by treatment of alkaline solutions with excess sulfur dioxide:

SO2 + NaOH NaHSO3

HSO3 is the conjugate base of sulfurous acid, H2SO3:

H2SO3 HSO3 + H+

Sulfurous acid is not an isolable compound and does not appear to exist in solution either.
An equilibrium that is much more consistent with spectroscopic evidence is given :

SO2 + H2O HSO3 + H+

HSO3 is a weak acidic species with a pKa of 6.97. Its conjugate base is the sulfite ion,
SO32:

HSO3 SO32 + H+

Bisulfites are reducing agents, as are all sulfites and sulfur dioxide, which contains
sulfur in the same oxidation state (+4).

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 eithersulfites (SO32), or bisulfites (HSO3),
depending on the pH. The counter ion can
be sodium (Na+), calcium (Ca2+), potassium(K+), magnesium (Mg2+) or ammonium (NH4+).

History

The use of wood to make pulp for paper began with the development of mechanical
pulping in Germany by F.G. Keller in the 1840s.[1] Chemical processes quickly followed, first with J.
Roth's use of sulfurous acid to treat wood, followed by Benjamin Chew Tilghman's US patent on the
use of calcium bisulfite, Ca(HSO3)2, to pulp wood in 1867.[2] Almost a decade later in 1874 the first
commercial sulfite process|sulfite pulp mill was built in Sweden. It used magnesium as the counter
ion and was based on work by Carl Daniel Ekman.
By 1900 sulfite pulping had become the dominant means of producing wood pulp, surpassing
mechanical pulping methods. The competing chemical pulping process, the sulfate or kraft
process was developed by Carl F. Dahl in 1879 and the firstkraft mill started (in Sweden) in
1890.[2] The first sulphite mill in the United States was the Richmond Paper Company in Rumford,
Rhode Island in the mid-1880s. The invention of the recovery boiler by G.H. Tomlinson in the early
1930s [1]allowed kraft mills to recycle almost all of their pulping chemicals. This, along with the ability
of the kraft process to accept a wider variety of types of wood and produce stronger fibers [3] made
the kraft process the dominant pulping process starting in the 1940s.[2] Sulfite pulps now account for
less than 10% of the total chemical pulp production[2] and the number of sulfite mills continues to
decrease.[4][5][6]

Magnesium was the standard counter ion until calcium replaced it in the 1950s.

The cooking liquor for the sulfite process is made by burning sulfur to form sulfur
dioxide, and absorbing the latter in water in the presence of calcium hydroxide or
carbonate. This causes the formation of calcium sulfite, which is relatively insoluble,
but which dissolves as calcium bisulfite when more sulfur dioxide is passed in. The
solution containing calcium bisulfite and an excess of sulfur dioxide forms the usual
cooking liquor, or "acid," for the sulfite process. In some plants a high magnesia
lime, containing about 40 per cent magnesia, is used; in others a high calcium lime
which contains about 9295 per cent calcium oxide. An acid pre-pared with a
sodium base instead of calcium can be used equally well, and even has an
advantage in cooking those woods which do not permit ordinary acid to penetrate
easily. An all-magnesia base acid is being used in a few mills, as is also an
ammonia base acid. These last threesoda, magnesia and ammoniaenable the
waste liquors to be treated for recovery of the base constituent, and so aid in
avoiding stream pollution, which is becoming a more and more serious problem.

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.
 The cooking liquor is prepared by adding the counter ions as hydroxides or
carbonates. The relative amounts of each species present in the liquid depend
largely on the relative amounts of sulfurous used. 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

Pulping Sulfite pulping is carried out between pH 1.5 and 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 (266 to 320 F), again
depending on the chemicals used.
Most of the intermediates involved in delignification in sulfite pulping are resonance-
stabilized carbocations formed either by protonation of carbon-carbon double bonds or acidic
cleavage of ether bonds which connect many of the constituents of lignin. It is the latter reaction
which is responsible for most lignin degradation in the sulfite process.[1] The electrophiliccarbocations
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.

COOKING LIQUOR the fresh pulping liquor for the sulfite process, consisting of a
mixture of SO2 together with one of the bases (alkali ions).
BROWN (or red) LIQUOR is the waste liquor from the sulfite pulping process.

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. Recent developments in Chemrec's black liquor gasification process,
adapting the technology to use in the sulfite pulping process, could make second generation
biofuels production an alternative to the conventional recovery boiler technology.[7]

The sulfite process can use calcium, ammonium, magnesium or sodium as a base.

Sodium bisulfite solution is a variously colored liquid at room temperature. It is used in waste
water treatment, in the pulp and paper industry, in the photographic industry and in various
other industries as a bleach or dechlorinator. It can also be used to treat flue gases to remove
sulfur trioxide (SO3). Sodium bisulfite solution is sometimes used as a food additive. Sodium
bisulfite solution can also be used in the manufacture of other chemicals.