SULFITE PULPING

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+).

Slfite pulping follows many of the same steps as Kraft pulping. However, sulfite pulp remains an important
commodity for specialty papers and a source for non-paper applications and cellulose ether derivatives. Compared
with the kraft pulping (sulfate process) sulfite pulping is not as versatile. The pulp itself is bright and easy to bleach.
However, the suitable wood species are limited. For instance, it is not possible to use pine as the raw material.

Sulfite process involves 2 types of reactions:

a. The hydrolytic splitting of the cellulose

b. The reaction of lignin with bisulfate

i. Acid sulfite

Under acidic conditions, the object is to solubilize lignin through the addition of hydrophillic sulfonate groups
(sulfonation).

ii. Neutral sulfite

Most often neutral sulfite pulping is used in association with mechanical pulping (Neutral Sulfite Semi Chemical-
NSSC). The purpose here is mainly to soften the lignin.

iii. Alkaline sulfite

The goal is sulfonation and fragmentation.

Coniferous; must be of good color and free of phenolic compounds

Cellulosic material
Spruce Hemlock tree Balsam tree

Principal reaction in digester RC:CR + Ca(HSO3)2 (RCHCRSO3)2Ca

Composition of cooking liquor 7% by weight of SO2, of which 4.5% is combined as sulfurous acid and
2.5% as calcium or Mg(HSO3)2. Cooking 1 t of pulp requires 175-220 kg of
SO2 and 55-68 kg of MgO.

Time: 6-12 h;
Cooking conditions
Temp: 125-160C or higher;

Pressure: 620-755 kPa

Chemical recovery SO2 relief gas recovered; magnesium liquor recovered and reused after
wood digestion and pulp washing
 Pulp characteristics
Dull white color; easily bleached; fibers weaker than kraft

White grades: book paper, bread wrap, fruit tissue, sanitary tissue
Typical paper products
Book paper Bread wrap

Fruit tissue Sanitary tissue

APPLICATIONS

Dissolving pulp is used in production of regenerated cellulose. The cellulose is dissolved in an organic
solvent and processed to regenerate the cellulose fibers in different forms.

As a raw material of cellulose derivatives, dissolving pulp is used in carboxymethyl cellulose (CMC), methyl
cellulose (MC), hydroxypropyl cellulose (HPC), hydroxyethyl cellulose (HEC), etc.

Since dissolving pulp is highly refined, it is a product of high whiteness with few impurities making it
suitable in specialty paper-related products such as filter paper and vulcanized fiber.

The 90-92 % cellulose content sulfite pulps are used mostly to make textiles (like rayon) and cellophane.
The 96-% cellulose content sulfate pulps are used to make rayon yarn for industrial products such as tire cord, rayon
staple for high-quality fabrics, and various acetate and other specialty products.

Cellulose powder is dissolving pulp that has undergone acid hydrolysis, been mechanically disintegrated
and made into fine powder.

ACID SULFITE COOKING LIQUOR PRODUCTION

Any sulfur that is vaporized in the burner enters a combustion chamber, where it is oxidized to sulfur dioxide.

The SO2 obtained is cooled quickly in a horizontal, vertical, or pond cooler consisting of a system of pipes
surrounded by water.

The liquor contains a certain amount of free sulfur dioxide.

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 160C (266 to 320F) again depending on the chemicals used.

The purpose of pulping is to reduce wood (or other fibrous raw material) to individual cellulose fibers. A
non-fibrous constituent of wood, lignin, binds cellulose fibers together, and is primarily responsible for reducing
paper quality and permanence. The sulfite process, the older and less used of the two primary chemical pulping
processes, cooks wood chips in sulfurous acid combined with limestone to produce calcium bisulfite.
 All processes used for pulping have the same goal- to release the fibrous cellulose from its surrounding
lignin while keeping the hemicelluloses and celluloses intact, thereby increasing the yield of useful fibers.

MANUFACTURING PROCESS

1. DEBARKING

It is the process of removing barks from the timber woods. The present trend in the wood and pulp industry is
to debark and size the logs on the site of the lumbering operations, then ship the pulp chips and logs to their
respective processing facilities off-site. A debarker is a machine used to strip or remove bark from logs before
processing.

2. CHIPPING

It is the process of turning debarked woods into finer woodchips. The objective is to fissure chips along the
grain, improving the penetration of cooking liquor for efficient delignification. A chipper is a machine used to chip
whole trees, branches, debris, mulch and other types of foliage.

3. FILTERING

It is the process of separating large wood chips from small wood chips. The more uniform chip and higher
yields result in fewer cooks for the same amount of pulp and may also result in reduced energy consumption in
both the digester and the evaporator in chemical pulping. A screen is used to filter and separate different sizes of
raw and different sizes of raw and crushed rock

4. WASHING

It is the application of water for getting the fiber. Pulp washers are essential to fiber line performance as the
pulp needs to be washed at almost all stages of the process. The washing result at one stage affects all the
subsequent stages.

5. //DIGESTION

It is the process of extracting lignin from wood chips. Pulp digester is used for extracting lignin from wood chips
in order to get only the fiber needed for the production of pulp. Here, the wood chips with water is treated with
the acid sulfite liquor.

6. //BLENDING

It is the process of stirring the mixture and commonly used together with filtering while constantly spinning.
Hydrapulpers, used mainly for handling waste paper, are fitted with special devices for removing unwanted
contraries such as wire, plastic, paper clips, etc.

When the bales of wood pulp or waste paper arrive at the paper mill, they are loaded onto a conveyor and
passed into a circular tank containing water. This has a very powerful agitator at the bottom which breaks up the
bales into small pieces.

7. FILTERING

It is the process of getting the pulp by passing a pair of filtering cloths and belts through a system of rollers.
Filters are used to get the pulp, which is then transported to the rollers to flatten it for storage. The pulp product
here is commonly used for paper.
/CHEMICAL RECOVERY

the chemicals separated from the pulp in the washers may or may not go into a recovery process. Chemical
recovery in sulfite pulping is practiced only if it is economical. If chemical recovery does occur the liquor goes
through an evaporator and then to a recovery furnace. Here, smelt is not formed, but ash and SO2 are formed.

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).

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

Calcium-based

Initially calcium was the preferred base because it was cheap and convenient to use as it obtained as
inexpensive calcium carbonate. However, no recovery system is available for this base, so most calcium base
mills either have ceased operation or have converted to sodium, magnesium or ammonium for which recovery
systems are available. For calcium based liquor, the gas is passed through towers packed with limestone with water
flowing down through the tower.

Because of the limited solubility of calcium bisulfites Ca(HSO 3)2, the pH of the liquor is very low (about 2)
and free sulfurous acid is present. This usually is called acid sulfite process. Because solution of Na, Mg and NH 4
bisulfite are all soluble at pH 4.5, the current practice is to pulp at higher pH, which is usually called bi-sulfite
pulping. Extremely long cooking times(7-10h) are necessary with acid sulfites whereas 4-5h is sufficient with bi-
sulfites.

Ammonia-based

Ammonia-based processes do not allow recovery of the pulping chemicals since ammonia or ammonium
salts are oxidized to nitrogen and nitrogen oxides when burned. As long as aqueous NH3 remains low ion price,
this process will be attractive.

Magnesium-based

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 sulfur dioxide from the flue
gases producing a magnesium bisulfite solution that is clarified, filtered and used as the pulping liquor. Mg(OH)2
+ 2 SO2 Mg(HSO3)2

Sodium-based Sodium base is the easiest to prepare (NaCO3 or NaOH usually is used as the make-up chemicals)
and gives the highest quality pulp; however, recovery processes though available, are complicated and expensive.
Sodium-based processes use a recovery system similar to that used in the kraft recovery process, except that
there is no lime cycle.