Kraft pulping process

Definition: It is a chemical pulping process that uses an alkaline solution of sodium

hydroxide (NaOH) and sodium sulphide (Na₂S) to break down wood fibers. It is also known
as sulphate pulping process.

Introduction

The Kraft pulping process is a widely used chemical method for converting wood into wood
pulp, which is then used to produce packaging and high strength papers and boards. Kraft
process dominates the industry because of advantages in chemical recovery and pulp
strength. It involves several chemical reactions that break down lignin, the substance that
binds cellulose fibers together in wood.

Process overview: Kraft process is a cyclical, self-sustaining, alkaline process. As a result of

process, a byproduct called black liquor is formed.

 Wood chips are first cooked in the alkaline cooking liquor (white and black liquor) in
a pressurized vessel or digester, where they are subjected to high temperatures and
pressures for several hours.
 The cooking process breaks down lignin, some hemicellulose and other impurities in
the wood chips, separating the fibres from each other and producing brown pulp.
 The brown pulp then washed and screened to remove any impurities and chemicals.
The pulp may undergo additional refining or bleaching steps to achieve the desired
quality and properties.
 The final pup is then sent to the paper machine for further processing into paper or
other products.

Chemicals Used

The primary chemicals used in the Kraft process are:

1. Sodium hydroxide (NaOH)

Sodium hydroxide (NaOH), a corrosive white crystalline solid that contains the Na + (sodium)
cation, the OH− (hydroxide) anion. It readily absorbs moisture until it dissolves. Sodium
hydroxide is the most widely used industrial alkali and is often used in drain and oven
cleaners.

2. Sodium sulphide (Na₂S)

Sodium sulphide (Na2S) is an inorganic chemical compound used in various industries,
including textiles, paper, leather, and water treatment. It has a strong odour resembling rotten
eggs and is soluble in water. It is also used in chemical manufacturing processes such as the
production of rubber chemicals, sulphur dyes, and oil recovery.

Raw materials:

 Wood, Bamboo, Bagasse, recycled paper, Agri residue

 NaOH, Na2S, Na2CO3 (white cooking liquor)
 Chlorine, hydrogen peroxide (as bleaching agents)

Pulping Process: the following steps are involved in pulping process;

1. Debarking: it is a crucial first step where bark is removed from logs to improve pulp
quality and process efficiency. Debarking is typically achieved using mechanical methods
like drum debarkers or hydraulic debarkers, and the removed bark can be used as fuel.
2. Chipping: chipping of wood chips occurs in Chipper bin. it has rotary disk with heavy
knife to reduce the size of wood chips up to 2-5 cm flat chips.
3. Impregnation: The chips are first wetted and preheated with steam. Cavities inside fresh
wood chips are partly filled with liquid and partly with air. The steam treatment causes
the air to expand and about 25% of the air to be expelled from the chips. The next step is
to saturate the chips with black and white liquor. Air remaining in chips at the beginning
of liquor impregnation is trapped within the chips.
4. Digestion/ Cooking: The wood chips are then cooked in pressurized digesters. Some
digesters operate in a batch manner and some in a continuous process. Typically,
delignification requires around two hours at 170 to 176 °C (338 to 349 °F). Under
digesting conditions, lignin and hemicellulose degrade to give fragments that are soluble
in the strongly basic liquid. The solid pulp (about 50% by weight of the dry wood chips)
is collected and washed. At this point the pulp is known as brown stock because of its
color. The combined liquids, known as black liquor.
 A net reaction in depolymerization of lignin by SH− (Ar = aryl, R = alkyl groups).

5. Chemical recovery system: the weak black liquor separated from the pulp by washing, is
sent to the kraft recovery system, where the inorganic pulping chemicals are recovered for
reuse, while the dissolved organics are used as fuel to make steam and power. The
recovery boiler also generates high pressure steam which is fed to turbogenerators,
reducing the steam pressure for the mill use and generating electricity.

Fig.: kraft pulping process

6. Blowing: The finished cooked wood chips are blown to a collection tank called a blow
tank, through blow down valve thar reduces the pressure of steam from 80 atm to 1 atm.
This releases a lot of steam and volatiles. The volatiles are condensed and collected.
7. Screening: Screening of the pulp is a process whereby the pulp is separated from large
shives, wood knots, dirt and other debris or undigested residues. The accept is the pulp.
The material separated from the pulp is called black liquor/reject, which undergo
chemical recovery process to make white liquor and inserted into digester tower.
8. Washing: The brown stock from the blowing goes to the washing stages where the used
cooking liquors are separated from the cellulose fibers. Normally a pulp mill has 3-5
washing stages in series. Several types of washing equipment are in use: Pressure
diffusers, Atmospheric diffusers, Vacuum drum washers, Drum displacers, Wash presses.
The dilution factor is the measure of the amount of water used in washing compared
with the theoretical amount required to displace the liquor from the thickened pulp.
Lower dilution factor reduces energy consumption, while higher dilution factor normally
 gives cleaner pulp. Thorough washing of the pulp reduces the chemical oxygen demand
(COD).
9. Bleaching: In a modern mill, brown stock (cellulose fibers containing approximately 5%
residual lignin) produced by the pulping is first washed to remove some of the dissolved
organic material and then further delignified by a variety of bleaching stages. In the case
of a plant designed to produce pulp to make brown sack paper or linerboard for boxes and
packaging, the pulp does not always need to be bleached to a high brightness. Bleaching
decreases the mass of pulp produced by about 5%, decreases the strength of the fibers and
adds to the cost of manufacture.
10. Paper making mill: After washing or bleaching, pulp sent to the mills for further
processing to making different types or papers or paper products.

Chemical Reactions involved in Kraft process

1. Digestion:
 Lignin Degradation

o Lignin is made up of phenolic and ether linkages. The alkaline conditions (high pH)
provided by NaOH and Na₂S break ether bonds (β-O-4 linkages) in lignin.
o Sodium sulfide (Na₂S) donates HS⁻ (hydrosulfide ions), which help cleave lignin’s
bonds more efficiently than NaOH alone.

o
  Hemicellulose Breakdown (Partial)
o Hemicellulose is partly hydrolyzed under alkaline conditions.

o Some sugars are degraded, contributing to the organic content of the waste streams.

Fig.: chemistry of Kraft pulping process

 Black liquor Formation: the spent cooking liquor (after pulping) is called black
liquor. It contains

o Dissolved lignin fragments

o Degraded hemicellulose
o Spent chemicals (NaOH, Na₂S)
o Inorganic compounds (Na₂CO₃, Na₂SO₄, etc.)
2. Chemical Recovery process:

Objectives:
o To minimize waste and cost:
o Black liquor is burned in a recovery boiler.
o This recovers white liquor chemicals and generates energy by process called smelting.
o Na₂CO₃ is converted back to NaOH using lime (CaO) in a process called causticizing
Reactions: The excess black liquor contains about 15% solids, is concentrated in a multiple
effect evaporator. After the first step the black liquor has about 20–30% solids. The weak
black liquor is further evaporated to 65% or even 80% solids ("heavy black liquor") and
burned in the recovery boiler to recover the inorganic chemicals for reuse in the pulping
process.
Smelting (recovery boiler): During combustion, delignification of the mixture occurs and
also sodium sulfate is reduced to sodium sulfide by the organic carbon in the mixture. The
resulting solution of sodium carbonate and sodium sulfide is known as "green liquor".

2NaR + air → Na2CO3 + CO2 Na2SO4 + 2C → Na2S + 2CO2 (from R)

(lignin)

Causticizing Reaction: This green liquor is then mixed with CaO, which
becomes Ca(OH)2 in solution, to regenerate the white liquor used in the pulping process,

Na2CO3 (aq) + Ca(OH)2 (s) → 2NaOH (aq) + CaCO3 (s)

(green liquor) (white liquor)

Calcium carbonate precipitates from the white liquor and is recovered and heated in a lime
kiln where it is converted to calcium oxide (lime). CaCO3 → CaO + CO2

Calcium oxide (lime) is reacted with water to regenerate the calcium hydroxide used as white
liquor. CaO + H2O → Ca(OH)2
Fig.: Kraft pulping process