Paper and Pulp

Paper
▪ Wood is the principal source of cellulose.(cotton,linen rags,and waste can also be
used)
▪ Bagasse ,straw, jute etc can also be used as raw materials.
▪ Disintegration of bulky fibrous materials into individual agglomerate fibres -pulping
▪ The Fibrous material used should have high cellulose content and low lignin content.
▪ There are two distinct phases in the conversion of raw wood into the finished paper
These are
(1) the manufacture of pulp from the raw wood
(2) the conversion of the pulp to paper itself.
Pulping process
▪ Pulp is derived from bamboo, bagasse, wood etc.
▪ Mechanical , chemical or semi-chemical methods

▪ Mechanical-debarked wood is shredded to form fibres

▪ Chemical- cellulose from wood is freed from lignin and other non cellulose
ingredients. Sulfate(kraft) and sulphite pulping process(40-65%yield)
▪ Semichemical –wood chips are given a mild chemical treatment with sulphite,
sulphate,caustic soda(65-90% yield)
Sulfate or Kraft pulp process
▪ NaOH,Na2S,Na2CO3 are the chemicals used
▪ Digestion(hydrolysis and solubilisation of lignin)
▪ R-R’+ NaOH R’’COONa + ROH
▪ R-R’ + Na2S mercaptans
▪ Chemical recovery from black liquor
▪ Smelting furnace
▪ 2NaR + air Na2CO3 + CO2
▪ Na2SO4 + 2C Na2S + 2CO2
▪ Causticizing
▪ Na2CO3 + Ca(OH)2 2NaOH + CaCO3
CaCO3 CaO + CO2
CaO + H2O Ca(OH)2
▪ Debarked logs are cut and send to chippers where they are reduced to chips of preselected size.
▪ The chips are then sent to a preheater through a star valve.
▪ From the preheater, the recirculating digestion liquor transfers the chips to the upper part of the
digestion tower.
▪ Chips flows down through a series of circumferential screen plates.
▪ Digestion is done to free lignin and other non-cellulosic content.
▪ Cooking time is about one and a half hours at 170°C.
▪ Cooking liquor (containing essentially sodium sulfide and caustic soda) is withdrawn as side stream and
circulated through external heat exchangers.
▪ Digested chips are cooled at base of the tower to avoid weakening of fibres by injection of cold black
liquor.
▪ A blow down valve reduces the pressure from 80atm to 1atm.
▪ The pulp liquor slurry is passed throgh the valve to blow tank.
▪ In the blow tank, heat is recovered in the form of steam.
▪ The blow tank has high concentration of pulp and low concentration of water.
▪ Pulp is screened to remove wood knots and filtered to remove black liquor (The spent cooking liquor
-black liquor).
▪ The brown pulp is either sent for bleaching or for finishing operations.
▪ Bleaching is done to remove colour residue and make white paper.
▪ Bleaching can be accomplished by using oxidizing agents or reducing agents.
▪ Reducing agents include dithionate, sodium borohydride or bisulfite.
▪ Oxidative bleaches include chlorine, ozone, Na2O2,H2O2,and ClO2
▪ Chlorine bleaching produces dioxins and other undesirable components.
▪ Hence chlorine was replaced by hydrogen peroxide.
▪ Chemical recovery from black liquor
▪ 2NaR + air Na2CO3 + CO2
▪ Na2SO4 + 2C Na2S + 2CO2
▪ Causticizing
▪ Na2CO3 + Ca(OH)2 2NaOH + CaCO3
CaCO3 CaO + CO2
CaO + H2O Ca(OH)2
 Recovery of chemicals
▪ The black liquor removed from the pulp contains 95 to 98 percent of the total alkali
charged to the digester.
▪ Using multiple effect evaporators and disc evaporator, the black liquor is concentrated
from a solid concentration of 15-18% to 60%.
▪ Makeup alkali is supplied by adding sodium sulfate.
▪ Organic carbon burns in the smelting furnace and an inorganic molten slag is produced.
▪ The smelt is made to fall in a dissolver where it is contacted with cold water to yield
green liquor.
▪ Insoluble impurities are settled out.
▪ Lime is added to the clear liquid and thereby CaCO3 is produced.
▪ CaCO3 formed is filtered off and the remaining liquid is called white liquor.
▪ This white liquor is returned to the digestor.
▪ White liquor washes out lignin
▪ White liquor + lignin black liquor
▪ Black liquor green liquor
▪ Green liquor white liquor
Sulphite pulping process
▪ Spruce is the most commonly used wood,(hemlock and balsam are also used)
▪ Essential reactions
▪ S+O2 SO2
▪ 2SO2 +H2O + CaCO3 Ca(HSO3)2 +CO2
▪ 2SO2 +H2O +MgCO3 Mg(HSO3)2 + CO2
▪ 2SO2 + Mg(OH)2 Mg(HSO3)2
▪ SO2 + H2O + NH3 NH4HSO3
▪ The cleaned wood chips of about 1.5 cm length is sent to storage bins above the digester.
▪ Wood is digested in an aq solution containing calcium bisulphite and excess of SO2.
▪ Two principal type of reaction in sulphite process are
1. Sulfonation and solubilizing of lignin with bisulphite.
2. Hydrolytic splitting of cellulose-lignin complex.
▪ Disposal of waste liquor creates serious water pollution problem.
▪ Sulphite process based on magnesium sulphite is more acceptable than calcium bisulphite.
▪ The cooking liquor is pumped at the bottom of the digester.(special acid resisting lining is given to
avoid corrosive action of cooking liquor)
▪ Digester is heated with direct steam.
▪ Temperature varies from 170-176oC and cooking time ranges from 6-12hours.
▪ At the end of digestion , the pulp is sent to a blown tank where it is washed with fresh water. The
weak red liquor is sent for chemical recovery.
▪ The pulp is pumped from blown tank to a series of screens where wood knots and large fibre lumps are removed
▪ This is then sent to centrifuges to remove foreign matter.
▪ The relatively pure pulp is concentrated in thickeners.
▪ Pulp is sent to bleaching where chlorine dioxide is added.
▪ Once chlorine is exhausted, milk of lime is added to neutralize the mass.
Recovery of chemicals
▪ The red liquor is evaporated and burnt in a boiler.
▪ MgO and SO2 are formed.
▪ Sulphur is melted in tank heated by rotary burner and is sent to burner where it undergoes oxidation to form
sulphur dioxide.
▪ Sulphur dioxide obtained is cooled quickly in a pond cooler consisting of a system of pipes surrounded by water.
▪ Absorption of gas in water in presence of Ca, Mg or ammonium compounds is accomplished in a series of two or
more absorption tanks.
▪ SO2 is blown up through the tower while fine spray of suspension is passed counter currently
▪ MgO is slaked to produce mg(OH)2 and pumped into cooling and acid tower and regained SO2 is supplied from
bottom.
▪ Fresh bisulfite liquor is finally formed.
▪ The final liquor charged on the digester contains calcium, magnesium or ammonium bisulphites, 4.5% SO2.
 Technical difference between sulfate
and sulphite pulping process
•i) Sulfate process is an alkaline process whereas the Sulfite process is an acidic
process.
ii) The pulp has to be bleached more in the Sulfate Process as compared to the
Sulfite process.
iii) For Sulfate process, digestion time is 2-5hrs at temperature 170-176°C and
pressure 660- 925kPa whereas for Sulfite process, time required is 6-12hrs at
temperature 125-160°C and pressure 620-755kPa.
iv) Raw materials are less significant and fibers have better strength properties
in Sulfate process.
Stock preparation
▪ Pulp from bleaching section goes to stock preparation section.
▪ Pulp fibres undergo physical and chemical treatments which make them suitable for making
paper.
▪ The main steps involved are:
o Receiving suspension from paper mill
o Thickening and storage
o Beating
o Blending of non-fibrous additives
o Stock storage
o Blending of paper broke
o Refining and supply to paper machine.
 ▪ Major functions in stock preparation are
1. Fibrillation and hydration of fibres
2. Cutting of fibres to desired length
Fibrillation helps in developing the strength characteristics of fibre.
Hydration helps fibres to hold water and increases the area.
Beating and refining is done to develop good fibre bonding and higher mechanical strength.
Beating is application of mechanical force on fibres to develop fibrillation and cutting.
Refining further improves the formation in paper machine.
Colouring material, fillers such as china clay and TiO2 and sizing materials are added to the
beater.
Sizing imparts water resistance to the paper and adds glaze. Size is prepared by cooking
rosin in water
After emulsion is thoroughly mixed with pulp, it is coagulated by adding 4percent alum
solution.
Paper making
▪ Paper making is usually done in fourdrinier machine
▪ Conversion of fibre suspension to paper sheet incorporates 3 steps
1. Random arrangement of fibres into a wet web.
2. Removal of free water from wet web by pressing and compaction of the sheet.
3. Removal of additional water by heated rolls.
Beater consists of rotating drum with metal blades mechanically disintegrates the pulp fibres and
makes paper uniform, dense and strong.
▪ A wet sheet is formed by running water-fibre slurry evenly onto a moving endless belt of wire cloth.
▪ Water drains by gravity, a part is next removed by pressure roll and then suction rolls.
▪ The white water obtained is reused to obtain maximum recovery of chemicals.
▪ The wet paper sheet containing 80% water is fed via felt roll to press section where water is
removed by mild pressure application.
▪ Sheet from press section is passed through smooth rolls and series of steam heated metal cylinders
▪ The sheet leaves the drying rolls with a moisture content of 5-6%.
▪ It is then passed through final series of pressure or calendaring rolls to produce a smooth well
finished paper.